NCD980602163_19961210_Warren County PCB Landfill_SERB C_Dioxin-Furan Sampling & Costs (File 1, 1994 - 1996)-OCR

State of North Carolina
Department of Environment,
Health and Natural Resources
Division of Epidemiology
James B. Hunt, Jr., Governor
Jonathan B. Howes, Secretary
M ichael Moser, M.D., M.P.H.
MEMORANDUM
TO: Bill Meyer, Director
December 10, 1996
Division of Waste Management .
THROUGH: Stanley Music, M.D., DTPH (LOND.), Chief. ~
Occupational and Environmental Epidemiology Sectio~
William J. Pate, Head
Medical Evaluation and Risk Assessment Branch
Occupational and Environmental Epidemiology Section
FROM: Luanne K. Williams, Pharm.D., Toxicologist/{ l,,\r
Medical Evaluation and Risk Assessment Branch
Occupational and Environmental Epidemiology Section
SUBJECT: Review of Dioxin Cleanup Levels for the Warren County PCB Landfill
Proposed by Hirschhorn & Associates
I have reviewed the document prepared by Dr. Joel Hirschhorn titled "Cleanup Levels
for Dioxin Contaminated Soils." My recommendations with regard to the derivation of
cleanup levels for dioxins and furans and sampling are as follows:
1. Dr. Hirschhorn has proposed 2 to 4 parts per trillion (ppt) as the residential cleanup level
based upon a target excess cancer risk of 1 x 10-s (one in a million). The recommended
target cleanup level for dioxin will be dependent upon the current or future use of the
site, use of the groundwater, and background concentrations. Guidance for determining
the target cleanup level for 2,3,7,8-TCDD (dioxin) is provided as follows:
RESIDENTIAL SOIL CLEANUP LEVEL
If the site is, or may be in the future, a residential area or in an area where activities of
sensitive human receptor populations occur (e .g., schools, day-care facilities, and
retirement centers), then the soil target concentration should be based on residential
exposure. The recommended soil cleanup level for 2,3,7,8-TCDD in a residential area is
4 ppt (USEPA Region Ill Risk-Based Concentration Table, April 1996). The oral slope
factor used to calculate 4 ppt was obtained from the USEPA 1995 Health Effects
Assessment Summary Tables. The oral slope factor was determined by USEPA based
P.O. Box 27687, Raleigh,
North Carolina 27611 -7687 N!JC
IINt't!ffl
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Bill Meyer
December 10, 1996
Page Two
upon the 1984, 1985, and 1989 review of the study Kociba RJ, Keyes DG, Bower JW et
al., 1978. "Results of a Two-year Chronic Toxicity and Oncogenicity Study of 2,3, 7,8-
Tetrachlorodibenzo-p-dioxin in Rats." Toxicol Appl Pharmacol. 46(2):279-303.
In 1984, the Centers for Disease Control (CDC) staff released a paper that contained
recommendations of 1 ppb or 1000 ppt as a level that would not likely result in adverse
effects in a residential area and according to CDC would correspond to an excess
cancer risk of 1 x1 o-6. Using the oral slope factor in the US EPA 1995 HEAST, a
residential soil dioxin concentration of 1000 ppt wo'uld correspond to a 2. 5 x 10-4 excess
cancer risk. It is recommended to use 4 ppt instead of 1000 ppt as a cleanup level in a
residential area.
INDUSTRIAL/COMMERCIAL SOIL CLEANUP LEVEL
If the site is, or may be in the future, an area where adult worker exposure occurs, then
the soil cleanup level should be based on industrial/commercial exposure. The
recommended soil cleanup level for 2,3,7,8-TCDD in an industrial/commercial area is 40
ppt (USEPA Region Ill Risk-Based Concentration Table, April 1996).
SOIL-TO-GROUNDWATER CLEANUP LEVEL
If the groundwat~r in this area is being used for drinking , then transport modeling may
be necessary to determine the maximum allowable dioxin soil concentration that would
not result in exceedance of the dioxin groundwater quality standard. If groundwater is
being used for drinking, then the soil cleanup level would be the lowest of the soil-to-
groundwater cleanup level; or the residential or industrial/commercial cleanup level
(whichever is applicable).
SOIL BACKGROUND CONCENTRATIONS
If the TCDD soil cleanup level is determined to be less than the soil background
concentrations, then it is recommended to use the soil background concentration as the
TCDD soil cleanup level. I have enclosed guidance for collecting background samples
which was obtained from USEPA 1989 Risk Assessment Guidance for Superfund
Volume I Human Health Evaluation Manual (Part A) (EPN540/1-89/002).
2. Dr. Hirschhorn & Associates are proposing higher toxicity equivalents factors (TEFs)
than those recommended by EPA for chlorinated dioxin and furan congeners. This
would result in lower cleanup levels. Higher TEFs are proposed to be used because of
the likelihood of synergistic effects from exposure to dioxins and polychlorinated
biphenyls (PCBs). I caution the use of higher TEFs because of the uncertainty in
synergism between dioxins/furans and PCBs. Also, I caution the use of higher TEFs
because conservative assumptions have already been considered in deriving the TCDD
carcinogenic slope factor and in deriving the exposure parameter values used to
Bill Meyer
December 10, 1996
Page Three
generate the TCDD cleanup level. The TEFs recommended by EPA and other state
should be used to determine cleanup levels for dioxin and furan congeners. A list of the
TEFs recommended by EPA is provided in Table 1 (USEPA 1995 Supplemental
Guidance to RAGS: Region 4 Bulletins Human Health Risk Assessment).
The soil cleanup level for each dioxin and furan congener found at the site can be
calculated by dividing the cleanup level for 2,3,7,8-TCDD by the appropriate TEF. If Dr.
Hirschhorn has scientific evidence to support different TEFs, then I would like the
opportunity to review it.
Table 1. Toxicity Equivalents Factors (TEF) for CDDs and CDFs*
Dioxin Compound TEF Furan Compound TEF
2,3,7,8-TCDD 1 2,3,7,8-TCDF 0.1
2,3,7,8-PeCDD 0.5 1,2,3,7,8-PeCDF 0.05**
2,3,7 ,8-HxCDD 0.1 2,3,4,7,8-PeCDF 0.5**
2,3,7,8-HpCDD 0.01 2,3,7,8-HxCDF 0.1
OCDD 0.001 2,3,7,8-HpCDF 0.01
Other CDDs 0 OCDF 0.001
Other CDFs 0
* Source: EPA, 1995. Supplemental Guidance to RAGS: Region 4 Bulletins Human Health Risk Assessment.
** Correction noted per telephone conversation with EPA Region 4 on November 27, 1996.
3. I have discussed the issues pertaining to this site with Dr. Renate Kimbrough with the
Institute for Evaluating Health Risks in Washington, D.C. She has expressed an interest
in reviewing the sampling protocol. She can be reached by phone at 202-289-8721 or
fax [phone]. Her address is as follows: Institute for Evaluating Health Risks, Suite
402, 1629 K Street N.W., Washington, D.C. 20006.
Please feel free to call me at any time. I can be reached at 715-6429. Thank you for
the opportunity to review the report.
LKW:lp
Enclosures
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. &EPA .·
United States ·
Environmental Protection·
Agency
Otf1ce of Emergency and
Remedial Response
Washington DC 20460
Super!und
Risk Assessment .. -..
Guidal1Ce fC>iSuperfur1CfltV
· Volume I
Human Health ·
Evaluation Manual
(Part A)
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REPRODUCED BY . . .
U.S. DEPARTMENT OF COMMERCE
NATIONAL TECHNICAL E
INFORMATION SERVICE
· SPRINGFIELD, VA 22161
If available, LSI (or ESI) data are especially useful
because they represent fairly extensive site studies.
~ofthe-e:cisting .. data, !h~
~s~_gr ~llQlllci formulate a conceptual model
of the site that identifies all poterit1aforsuspected
sources· of contamination, types and concentfatioris
of contaminants detected_ at_ the .. Site, _·pofomially
_contamin.l!t~ .. med_ia, and pqtential ·exposure
pathways, including receptors (see Exh1bit ~1).-
.. As discilssed previously, identification of potential
exposure pathways, especially the exposure points,
is a key element in the determination of data
needs for the risk assessment. Details concerning
development of a conceptual model for a site are
provided in the DQO guidance (EPA 1987a,b) and
the RI/FS guidance (EPA 1988a ).
In most cases, site information available at
the start of the RI/FS is insufficient to fully
characterize . the site and the potential exposure
pathways. The conceptual model developed at this
stage should be adequate to determine the
remaining data needs. The remainder of this
chapter addresses risk assessment data needs in
detail.
4.3 ADDRESSING MODELING
PARAMETER NEEDS
As discussed in detail in Chapter 6,
contaminant release, transpon, and fate models
are often needed to supplement monitoring data
when estimating exposure concentrations.
Therefore, a preliminary site modeling strategy
should be developed during RI/FS scoping to
allow model input data requirements to be
incorporated into the data collection requirements.
This preliminary identification of models and
other related data requirements will ensure that
data for model calibration and validation are
collected along with other physical and chemical
data at the site. Exlnoit 4-2 lists (by medium)
several site-specific parameters often needed to
incorporate fate and transpon models in risk
assessments.
Although default values for some modeling
parameters are available, it is preferable to obtain
site-specific values for as many input parameters
as is feasible. If the model is not sensitive to a
Page 4-5
panicular parameter for which a default value is
available, then a default value may be used.
Similarly, default values may be used if obtaining
the site-specific model parameter would be too
time consuming or expensive. For example,
cenain airborne dust emission models use a
default value for the average wind speed at the
site; this is done because representative
measurements of wind speed at the site would
involve significant amounts of time (i.e., samples
would have to be collected over a large pan of
· the year).
Some model parameters are needed only if
the sampling conducted at a site is sufficient to
suppon complex models. Such model parameters
may not be necessary if only simple fate and
transpon models are used in the risk assessment.
4.4 DEFINING BACKGROUND
SAMPLING NEEDS
Background sampling is conducted to
distinguish site-related contamination from
naturally occurring or other non-site-related levels
of chemicals. The following subsections define the
types of background contamination and provide
guidance on the appropriate location and number
of background samples.
4.4.1 TYPF.s OF BACKGROUND
There are two different types of background
levels of chemicals:
(1) naturally occurring levels. which are
ambient concentrations of chemicals
present in the environment that have not
been influenced by humans ( e.g.,
aluminum, manganese); and
(2) anthropogenic levels, which are
concentrations of chemicals that are
present in the environment due to
human-made, non-site sources ( e.g.,
industry, automobiles).
Background can range from localized to
ubiquitous. For example, pesticides -most of
which are not naturally occurring (anthropogenic)
-may be · ubiquitous in certain areas ( e.g.,
EXHIBIT 4-1
ELEMENTS OF A CONCEPTUAL EVALUATION MODEL
SOURCES
RECEPTORS
SOURCE: EPA 1987a
VARIABLES
• CONTAMINANTS
• CONCENTRATIONS
•TIME
• LOCATIONS
• MEDIA
• RATES OF MIGRATION
•TIME
• LOSS AND GAIN FUNCTIONS
• TYPES
• SENSITIVITIES
•TIME
• CONCENTRATIONS
• NUMBERS
HYPOTHESES TO
BE TESTED
• SOURCE EXISTS
• SOURCE CAN BE CONTAINED
• SOURCE CAN BE REMOVED
AND DISPOSED
• SOURCE CAN BE TREATED
• PATHWAY EXISTS
• PATHWAY CAN BE
INTERRUPTED
• PATHWAY CAN BE
ELIMINATED
• RECEPTOR IS NOT.
IMPACTED BY MIGRATION
OF CONTAMINANTS
• RECEPTOR CAN BE
RELOCATED
• INSTITUTIONAL CONTROLS
CAN BE APPLIED
• RECEPTOR CAN BE
PROTECTED
'
•
Page 4-7
EXHIBIT 4-2
EXAMPLES OF MODELING PARAMETERS FOR WIIlCH
INFORMATION MAY NEED TO BE OBTAINED DURING
A SITE SAMPLING INVESTIGATION
Type of Modeling
Source Characteristics
Soil
Ground-water
Air
Surface Water
Sediment
Biota
Modeling Parameters0
Geometry, physicaVchemical conditions, emission rate, emission
strength, geography
Particle size, dry weight, pH, redox potential, mineral class, organic
carbon and clay content, bulk density, soil porosity
Head measurements, hydraulic conductivity (pump and slug test
results), saturated thickness of aquifer, hydraulic gradient, pH,
redox potential, soil-water partitioning
Prevailing wind direction, wind speeds, stability class, topography,
depth of waste, contaminant concentration in soil and soil gas,
fraction organic content of soils, silt content of soils, percent
vegetation, bulk density of soil, soil porosity
Hardness, pH, redox potential, dissolved oxygen, salinity,
temperature, conductivity, total suspended solids, flow rates
and depths for rivers/streams, estuary and embayment
parameters such as tidal cycle, saltwater incursion extent,
depth and area, lake parameters such as area, volume, depth,
depth to thermocline
Particle size distribution, organic content, pH, benthic oxygen
conditions, water content
Dry weight, whole body, specific organ, and/or edible portion
chemical concentrations, percent moisture, lipid content,
size/age, life history stage
0 These parameters are not necessarily limited to the type of modeling with which they are
associated in this exhibit. For example, many of the parameters listed for surface water are also
appropriate for sediments.
Page 4-8
agricultural areas); salt runoff from roads during
periods of snow may contribute high ubiquitous
levels of sodium. Polycyclic aromatic
hydrocarbons (P AHs) and lead are other examples
of anthropogenic, ubiquitous chemicals, although
these chemicals also may be present at naturally
occurring levels in the environment due to natural
sources ( e.g., forest fires may be a source of
P AHs, and lead is a natural component of soils in
some areas).
4.4.2 BACKGROUND SAMPLING
LOCATIONS
Background samples are collected at or near
the haz.ardous waste site in areas not influenced
by site contamination. They are collected from
each medium of concern in these offsite areas.
That is, the locations of background samples must
be areas that could not have received
contamination from the site, but that do have the
same basic characteristics as the medium of
concern. at the site.
Identifying background location requires
knowing which direction is upgradient/upwind/
upstream. In general, the direction of water flow
tends to be relatively constant, whereas the
direction of air flow is constantly changing.
Therefore, the determination ~f background
locations for air monitoring requires constant and
concurrent monitoring of factors such as wind
direction.
4.4.3 BACKGROUND SAMPLE SIZE
In appropriate circumstances, statistics may
be used to evaluate background sample data.
Because the number of background samples
collected is important for statistical hypothesis
testing, at some sites a statistician should be
consulted when determining background sample
size. At all sites, the RPM should decide the
level of statistical analysis applicable to a
particular situation.
Often, rigorous statistical analyses are
unnecessary because site-and non-site-related
contamination clearly differ. For most sites, the
issue will not be whether a difference in chemical
concentrations can be demonstrated between
contaminated and background areas, but rather
that of establishing a reliable representation of the
extent (in three dimensions) of a contaminated
area. However, statistical analyses are required
at some sites, making a basic understanding of
statistics necessary. The following discussion
outlines some basic statistical concepts in the
context of background data evaluation for risk
assessment. (A general statistics textbook should
be reviewed for additional detail. Also, the box
below lists EPA guidance that might be useful.)
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.. iliry Study (EPA 1988d) . .
A statistical test of a hypothesis is a rule
used for deciding whether or not a statement (i.e.,
the null hypothesis) should be rejected in favor of
a specified alternative statement (i.e., the
alternative hypothesis). In the context of
background contamination at hazardous waste
sites, the null hypothesis can be expressed as
"there is no difference between contaminant
concentrations in background areas and onsite,"
and the alternative hypothesis can be expressed as
"concentrations are higher onsite.• This expression
of the alternative hypothesis implies a one-tailed
test of significance.
The number of background samples collected
at a site should be sufficient to accept or reject
the null hypothesis with a specified likelihood of
error. In statistical hypothesis testing there are
two types of error. The null hypothesis may be
rejected when it is true (i.e., a Type I error), or
not rejected when it is false (i.e., a Type II error).
An example of a Type I error at a hazardous
waste site would be to conclude that contaminant
concentrations in onsite soil are higher than
background soil concentrations when in fact they
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are not The corresponding Type II error would
be to conclude ·that onsite contaminant
concentrations are not higher than background
concentrations when in fact they are. A Type I
error could result in unnecessary remediation,
while a Type II error could result in a failure to
clean up a site when such an action is necessary.
In customary notations, o (alpha) denotes the
probability that a Type I error will occur, and fi
(beta) denotes the probability that a Type II error
will occur. Most statistical comparisons refer to
o, also known as the level of significance of the
test. If o = 0.05, there is a 5 percent (i.e., 1 in
20) chance that we will conclude that
concentrations of contaminants are higher than
background when they actually are not.
Equally critical considerations in determining
the number of background samples are fi and a
concept called·"power." The power of a statistical
test has the value 1 -fi and is defined as the
likelihood that the test procedure detects a false
null hypothesis. Power functions for commonly
used statistical tests can be found in most general
statistical textbooks. Power curves are a function
of o (which normally is fixed at 0.05), sample size
(i.e., the number of background and/or onsite
samples), and the amount of variability in the
data. Thus, if a 15 percent likelihood of failing
to detect a false null hypothesis is desired (i.e., fi = 0.15), enough background samples must be
collected to ensure that the power of the test is
at least 0.85.
A small number of background samples
increases the likelihood of a Type II error. If an
insufficient number of background samples is
collected, fairly large differences between site and
background concentrations may not be statistically
significant, even though concentrations in the
many site samples are higher than the few
background samples. To guard against this
situation, the statistical power associated with the
comparison of background samples with site
samples should be evaluated.
In general, when trying to detect small
differences as statistically significant, the number
of background samples should be similar to the
number of onsite samples that will be used for the
comparison(s) (e.g., the number of samples taken
from one well). (Note that this does not mean
Page 4-9
that the background sample size must equal the
total number of onsite samples.) Due to the
inherent variability of air concentrations (see
Section 4.6), background sample size for air needs
to be relatively large.
4.4.4 COMPARING BACKGROUND
SAMPLES TO SITE-REI.ATED
CONTAMINATION
The medium sampled influences the kind of
statistical comparisons that can be made with
background data. For example, air monitoring
stations and ground-water wells are normally
positioned based on onsite factors and gradient
considerations. Because of this purposive
placement (see Section 4.6.1), several wells or
monitors cannot be assumed to be a random
sample from a single population and hence cannot
be evaluated collectively (i.e., the sampling results
cannot be combined). Therefore, the information
from each well or air monitor should be compared
individually with background.
Because there typically are many site-related,
media-specific sampling location data to compare
with background, there usually is a "multiple
comparison problem• that must be addressed. In
general, the probability of experiencing a Type I
error in the entire set of statistical tests increases
with the number of comparisons being made. If
o = 0.05, there is a 1 in 20 chance of a Type I
error in any single test. If 20 comparisons are
being made, it therefore is likely that at least one
Type I error will occur among all 20 tests.
Statistical Analysis of Ground-water Monitoring
Data at RCRA Facilities (EPA 1989c) is useful
for designing sampling plans for comparing
information from many fixed locations with
background.
It may be useful at times to look at
comparisons other than onsite versus background.
For example, upgradient wells can be compared
with downgradient wells. Also, there may be
several areas · within the site that should be
compared for differences in site-related
contaminant concentration. These areas of
concern should be established before sampling
takes place. If a more complicated comparison
scheme is planned, a statistician should be
consulted frequently to help distribute the
sampling effort and design the analysis.
Page 4-10
A statistically significant difference between
background samples and site-related contamination
should not, by itself, trigger a cleanup action. The
remainder of this manual still must be applied so
that the toxicological --rather than simply the
statistical --significance of the contamination can
be ascertained.
4.5 PRELIMINARY IDENTIFI-
CATION OF POTENTIAL
HUMAN EXPOSURE
A preliminary identification of potential
human exposure provides much needed
information for the SAP. This a~'<lty_jnvolves
the identification of ...(1). media-o.L CQnce_m, _ (2)
areas of concern _(i.e,,_;eneral locations of the
media_ to be-sample4),. (3) types o_f ~he~cals
expected at the site, and ( 4) potential routes of
contaminant transport through _the_enyironment
(e.g., inter-media transfer, food chain).' -7rus
section provides general information on the
preliminary identification of potential human
exposure pathways, as well as specific information
on the various media. (Also, see Chapter 6 for
a detailed discussion of exposure assessment.)
4.5.1 GENERAL INFORMATION
Prior to discussing various specific exposure
media, general information on the following is
provided: media, types of chemicals, areas of
concern, and routes of contaminant transport is
addressed.
Media of concern (including biota). For risk
assessment purposes, media of concern at a site
are:
• any currently contaminated media to
which individuals may be exposed or
through which chemicals may be
transported to potential receptors: and
• any currently uncontaminated media that
may become contaminated in the future
due to contaminant transport.
Several medium-specific factors in sampling may
influence the risk assessment. For example,
limitations in sampling the medium may limit the
detailed evaluation of exposure pathways described
in Chapter 6. To illustrate this, if soil samples
are not collected at the surface of a site, then it
may not be possible to accurately evaluate
potential exposures involving direct contact with
soils or exposures involving the release of
contaminants from soils via wind erosion (with
subsequent inhalation of airborne contaminants by
exposed individuals). Therefore, based on the
conceptual model of the site discussed previously,
the risk assessor should make sure that
appropriate samples are collected from each
medium of concern.
Areas of concern. Areas of concern refer to
the general sampling locations at or near the site.
For large sites, areas of concern may be treated
in the RI/FS as "operable units," and may include
several media. Areas of concern also can be
thought of as the locations of potentially exposed
populations (e.g., nearest residents) or biota (e.g.,
wildlife feeding areas).
Areas of concern should be identified based
on site-specific characteristics. These areas are
chosen purposively by the investigators during the
initial scoping meeting. Areas of concern should
include areas of the site that:
(1) have different chemical types;
(2) have different anticipated concentrations
or hot spots;
(3) are a release source of concern;
(4) differ from each other in terms of the
anticipated spatial or temp(?ral variability
of contamination;
(5) must be sampled using different
equipment; and/or
(6) are more or less costly to sample.
In some instances, the risk assessor may want
to estimate concentrations that are representative
of the site as a whole, in addition to each area of
concern. In these cases, two conditions generally
should be met in defining areas of concern: (1)
the boundaries of the areas of concern should not
overlap and (2) all of the areas of concern
.....
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-r· \ ,, ("&. -· 7)• ~ f \-~I . !·-r" ( )'/~"' .,1. -~~ -~ To: From: Subject: Date: Mike Kelly1 Dioxin/Furan Bid Proposals for the Warren County PCB Landfill December 10, 1996 We received bid proposals for this RFP from five different companies for this RFP. I have summarized my review in the following tables. COST SUM:MARY TABLE LABNMvffi OVERALL COST STD QUICK ON SITE OVERNIGHT COST1 PERSAMP TAT2 TAT$ PERSON$ DEL. COST 1 -Triangle Labs $37,356.00 $849.00 30d 14 day: +10% $150/trip + No 7 day: +50% $60/hr/person Quote 2 -Midwest Research Institute $36,300.00 $825.00 45d 14 day: +27% $500/pickup No 7 day: +52% Quote 3 -Southwest Research Institute $32,912.00 $748.00 30d 14 day: +17% 1 person-2 days No 7 day: +40% $3,200 Quote 4-Maxim $28,820.00 $655.00 30d 14 day: +45% Cannot No 7 day: +133% Provide Quote 5 -Southwest Labs of Oklahoma $28,560.00 $630.00 (liq) 21d 14 day: +50% $3 8/hr/person + $15 $700.00 (soil) 7 day: +75% + $0.28/mile per 48 hours:+ 100% from Raleigh sample 1 Assumed 44 total samples; 2 TAT= Tum Around Time
,,.,, ... MISCELLANEOUS INFORMATION LAB NAME REFERENCES LEAD TIME CONTAINERS REPORTING NEEDED SIDPPING $ FORMAT 1 -Triangle Labs 6 provided 7 days Included in quote Example included w/ raw data 2 -Midwest Research Institute 5 provided Did not state Did not indicate Table summary format only 3 -Southwest Research Institute 81 provided Did not state Did not indicate Did not supply report example 4-Maxim 6 provided 7 days Included in quote Example included w/ raw data 5 -Southwest Labs of Oklahoma 5 Provided 7 days Included in quote Example included w/ raw data + confidential refs. Southwest Labs of Oklahoma provided the best overall proposal and the lowest cost. They had the most extensive reporting format and were the only one that was certified by North Carolina DEHNR (Lab # 404) and EPA (CLP). They were also able to supply on-site personnel during the sampling and had the best analytical results turn around time. Therefore, after extensive discussions with staff and the Science Advisors, we recommend that Southwest Labs of Oklahoma be awarded the contract for this RFP.
State of North Carolina
Department of Environment,
Health and Natural Resources
Division of Waste Management
James B. Hunt, Jr., Governor
Jonathan B. Howes, Secretary
William L. Meyer, Director
AVA
DEHNR
November 13, 1996
MEMORANDUM:
TO: Potential Respondents
From: Mike Kelly, Deputy Director
Division of Waste Managem
SUBJECT: REQUEST FOR PROPOSALS ON DIOXIN/FORAN TESTING
CHANGES IN RFP PCB LF-3
DUE DATE CHANGE FROM: NOVEMBER 22, 1996 12:00 NOON
TO: NOVEMBER 27, 1996 12:00 NOON
Attached is a new Part I and copies of Part III and Part IV. Please insert Part II, the scope
of work, into this RFP. The DEHNR revised its RFP format last month and we inadvertently
sent the older one to you. The Part II, Scope of Work did not change from the original one sent
to you last week.
In order to allow you time to evaluate this new material, we are extending the due date to
Wednesday, November 27, 1996, 12:00 noon. No further questions will be answered after 12:00
noon, Monday, November 25, 1996.
I apologize for any inconvenience this may have caused you.
P.O. Box 27687,
Raleigh, North Carolina 27611 -7687
Voice 919-733-4996 IGP®'MffiN
FAX [phone]
An Equal Opportunity Affirmative Action Employer
50% recycled/10% post-consumer paper
PROPOSAL NO. PCB LF-3 Issue Date: November 6, 1996
NC DEPARTMENT OF ENVIRONMENT HEALTH AND NATURAL
RESOURCES
DIVISION OF WASTE MANAGEMENT
Request for Proposal
for
Testing for Dioxin/ Furans
Closing Date: November 27, 1996
Send all proposals directly to:
Time: 12:00 noon
NC Department of Environment,
Health, and Natural Resources
Division of Waste Management
401 Oberlin Road, Suite 150
Raleigh, NC 27605
Attention: Michael A. Kelly
Please note the proposal number and closing date on the bottom left hand comer of your
envelope.
PART I
SOLICITATION INSTRUCTIONS
1.1 This request for proposals (hereinafter referred to as ("RFP") solicits proposals for
contractual services pursuant to Section 1 NCAC 5D.0300-.0509 of North Carolina
Administrative Code.
Mark outside of return envelopes: Reply to
1.2 Using Agency
The services solicited herein shall be performed for:
Department of Environment, Health, and Natural Resources
1.3 Issuing Agency
Department of Environment, Health, and Natural Resources
Division of Waste Management
401 Oberlin Road, Suite 150
Raleigh, North Carolina 27605
Attention: Michael A. Kelly
Telephone: [phone] Extension 201
1.4 Copies of this request for proposals will be distributed only by mail or they can be obtained
in person from Suite 150,401 Oberlin Road, Raleigh, NC 27605.
1.5 Sealed proposals subject to the terms and conditions made a part hereof will be received at
the address specified in 1.3 until 12:00 noon.
1.6 Refer technical inquiries to address/person specified in 1.3.
1.7 Pursuant to Article 3 and 3C, Chapter 143 of the North Carolina General Statutes and
Executive Order No. 77, the State invites and encourages participation in this procurement
by businesses owned by minorities, women and the disabled including utilization as
subcontractors to perform functions under this Request for Proposals.
1.8 Subcontracting: Offerers may propose to subcontract portions of the work provided that
their proposals clearly indicate what work they plan to subcontract and to whom and that
all information required about the prime contractor is also included for each proposed
subcontractor.
1.9 Performance and Default: The State reserves the right to require a Performance Bond or
other suitable performance guarantee from the successful offerer as provided by law
without expense to the State. In case of default by the contractor, the State may procure
the services from other sources and hold the Contractor responsible for any excess cost
occasioned therebv.
1.1 O Pricing: If either a unit price or an extended price is obviously in error and the other is
obviously correct, the incorrect price will be disregarded. The right is reserved to accept
other than the lowest priced proposal as may be determined to serve the best interest of
the State Agency.
1.11 Specifications: Any deviation from specifications indicated herein must be clearly pointed
out; otherwise, it will be considered that the proposal offered is in strict compliance with
these specifications, and the successful offerer will be held responsible therefor.
Deviations must be explained in detail on an attached sheet(s).
1.12 Exceptions: All proposals are subject to the terms and conditions outlined herein. All
responses will be controlled by such terms and conditions and the submission of other
terms and conditions and/or other documents as part of an offerer's response will be
waived and have no effect either on this Request for Proposals or on any contract that
may be awarded resulting from this solicitation. The attachment of other terms and
conditions by an offerer may be grounds for rejection of that offerer's proposal.
1.13 Award: All qualified Proposals will be evaluated and acceptance made on the
Proposal judged by the Contracting Agency to constitute the best value offered for the
purpose intended. Evaluation will be based on the offerers qualifications, experience,
similar related experience, past performance, financial standing, labor supply, hours
offered, references, cost and overall demonstrated ability to perform the service required.
The Contracting Agency reserves the right to contract with more than one offerer to
provide the services described herein.
1.14 No Bid/Offer: Unless a response, in the form of either a proposal or a written decline to
offer a proposal, is received, offerer's name may be removed from the applicable mailing
list.
1.15 Cost for Proposal Preparation: The State will not reimburse offerers for costs incurred in
the preparation and submission of a proposal.
1.16 Offerer's Representative for Business Purpose: The name, mailing address, and
telephone number of the offerer's authorized agent with authority to bind the firm and
answer official questions concerning the offerer's proposal must be clearly stated.
1.17 Time for Consideration: Preference may be given to proposals allowing not less than 30
days for consideration and acceptance.
1.18 Telegraphic Offers: Telegraphic, telecopy and facsimile offers will not be considered;
however, offers may be modified by such means, providing such notice is received prior
to the date and time of bid opening above specified, and provided a signed original
follows.
RF?# 3
1.19 Any explanation desired by an offerer regarding the meaning or interpretation of the RFP,
attachments, specifications, etc. must be requested in writing and with sufficient time
allowed for a reply to reach offerers before the submission of their offer. Oral explanation
of instructions given before the award of the contract will not be binding. Any information
given to a prospective offerer concerning the RFP will be furnished to all prospective
offerers as an amendment to RFP, if such information is necessary to offerers in
submitting offers on the RFP or if the lack of such information would be prejudicial to
uninformed off erors.
1.19.1 Acknowledgment of Amendments to RFP: Receipt by an offerer of an
amendment to this RFP must be acknowledged by including a copy of the
amendment with offerer's proposal.
1.20 The successful offerer shall provide adequate facilities, labor, equipment, services,
supervision and lay days to meet all conditions of the contract specifications.
1.21 Liability: The successful offerer shall assume liability for damage or loss resulting from
the wrongful act(s) and/or negligence of its employees while engaged in the performance
of the contract. The contractor or its insurer shall reimburse the Contracting Agency for
any such damage or loss within 30 days after a claim is submitted.
1.22 Insurance: The successful offerer shall at its sole cost and expense procure and
maintain in full force and effect during the term of the contract from an insurance
company duly authorized to do business In North Carolina, insurance as appropriate for
the conduct of the contract:
1.23
RFP#
1.22.1 Worker's Compensation Insurance covering all of contractor's employees who are
engaged in any work under the contract.
1.22.2 Public Liability Insurance in the amount of $300,000.00 and Property Damage
Insurance in the amount of $100,000 .00.
1.22.3 Automobile bodily injury and property damage liability insurance when the services
to be performed require the use of motor vehicles .
1.22.4 Fidelity bonding (Honesty Bonding)
Contractor shall furnish the State a certificate evidencing required insurance coverage
prior to commencing work. Ali certificates of insurance shall provide that the insurance
company will give customers fifteen (15) days written notice prior to cancellation or any
change in stated coverage of any such insurance. All insurance shall remain in effect for
the duration of the contract.
Failure to provide current Certificates of Insurance to the Contracting Agency as
required, during the term of this contract will be considered default and the contract
may be cancelled.
Laws: The contractor shall comply with laws, ordinances , codes , rules and regulations
bearing on the conduct of the work including Federal, State and local agencies having
jurisdiction. This shall include, but not be limited to, minimum wages, labor and equal
employment opportunity laws.
4
1.24
1.25
1.26
1.27
1.28
1.29
RFP#
Eac~ offerer is cautioned. that the State is not obligated to ask for or accept, after the
closing date for_ the receipt of proposals, data which is essential for a complete and
thorough ~~~luat1on of the proposals. The State of North Carolina may award a contract
based on m1t1al offers _received without discussion of such offers. Accordingly, each initial
off~r should be submitted on the most favorable and complete price and technical terms
which the offerer can submit to the State.
!he St~te. reserves the right to accept or reject any and all proposals; to waive any
!nformal1ty in proposals; and, unless otherwise specified by the offerer, to accept any item
m any proposal.
Confidentiality: In submitting its proposal the offerer agrees not to discuss or otherwise
reveal the contents of the proposal to any source outside of the using or issuing agency,
government or private, until after the award of the contract. Offerers not in compliance
with this provision may be disqualified, at the option of the State, from contract award.
Only discussions authorized by the issuing agency are exempt from this provision.
Proprietary Information: All proposals, after the award of the contract, will be open for
public inspection. Trade secrets or similar proprietary data which the offerer does not
wish disclosed to other than personnel involved in the evaluation or contract
administration will be kept confidential to the extent permitted by NCAC T01 :058.1501
and G.S. 132-1.2. Each page shall be identified in boldface at the top and bottom as
"CONFIDENTIAL". Any section of the proposal which is to remain confidential shall also
be marked in boldface on the title page of that section. Cost information and certain other
information essential to the evaluation of the proposal may not be deemed confidential.
Advertising: In submitting its proposal, the offerer agrees not to use the results therefrom
as a part of any news release or commercial advertising without prior written approval of
the Division of Purchase and Contract and the using agency.
Protest Procedures: A party wanting to protest a contract awarded pursuant to this
solicitation must submit a written request to the State Purchasing Officer, Division of
Purchase and Contract, 116 West Jones Street, PO Box 29582, Raleigh, NC 27626-
0582. This request must be received in the Division of Purchase and Contract within
thirty (30) consecutive calendar days from the date of the contract award, and must
contain specific sound reasons and any supporting documentation for the protest. NOTE:
Contract award notices are sent only to those actually awarded contracts and not to every
person or firm responding to this solicitation. Offerers may call (919) 733-97 46 to obtain
a verbal status of contract award . All protests will be handled pursuant to the North
Carolina Administrative Code, Title 1, Department of Administration, Chapter 5, Purchase
and Contract, Section 58.1519:
5
PART II
SCOPE OF WORK
PART II THE SCOPE OF WORK REMAINS THE SAME AS MAILED IN THE
NOVEMBER 5, 1996 PACKAGE, EXCEPT FOR THE DUE DATE AND THE CUT OFF FOR
QUESTIONS DATE. THE NEW DUE DATE IS 12:00 NOON ON WEDNESDAY,
NOVEMBER 27, 1996. THE CUT OFF DATE FOR QUESTIONS IS NOW 12:00 NOON ON
MONDAY, NOVEMBER 25, 1996.
PLEASE INSERT THE ORIGINAL PART II IN HERE.
PART Ill
TECHNICAL PROPOSAL
3.1 Each offerer responding to this RFP must submit three (3) copies of a statement of
technical qualifications, detailing the firms ability to perform the services required herein.
The technical proposal should be in narrative form and must include at a minimum the
information outlined below.
3.1 .1 Information relative to the offerer's background, experience, and such other
information as may be deemed relevant for the purpose of evaluation of
professional skills and capability.
3.1.2 Information describing the size and organizational structure of the offerer's firm.
3.1.3 Information describing how each requirement of the scope of work will be
addressed.
3.2 Each offerer must submit a list of client names, type of contract (including type of
services produced) and inclusive dates of contracts for similar work.
3.3 Each offerer shall propose a contract schedule and guaranteed completion date and shall
assure the Department that their firm is capable of maintaining the schedules and
meeting the deadlines that have been established. Any schedule and deadline, once
established by contract, can only be adjusted by mutual consenf of all parties thereto.
3.4 Each offerer must furnish complete professional services relating to the requirements of
the scope of work including materials and any necessary subcontractors. The bid price
offered will be a fixed price or fixed rate and shall include all professional fees for services
to be rendered as well as all incidental travel and production expenses.
RFP# 7
PART IV
FORM OF PROPOSAL
The undersigned bidder proposes and agrees if this proposal is accepted to contract with the
Department of Environment, Health, and Natural Resources, Division of to furnish the services
required herein, and to complete the scope of work as described in Part II hereof. Services should be
accomplished in full and complete accordance with the specifications and contract documents to the full
and entire satisfaction of the Division of , with a definite understanding that no money will be allowed
for extra work except as may be set forth in written addendum to the contract, duly executed by all
parties thereto.
The parties hereto agree that in consideration for performing all the requirements hereunder, DEHNR
shall pay the offerer S · or per the attached cost proposal for the services as described
herein, said sum to be full and complete compensation for the offerer's services required herein .
Pursuant to the provisions of G.S. 143-54, and under penalty of perjury, the signer of this proposal
certifies that this proposal has not been arrived at collusively nor otherwise in violation of Federal nor
North Carolina antitrust laws.
Name of Firm or Corporation submitting bid
Federal 1.0. Number ______________________________ _
By: _________________________ ___;____; _______ _
Typed Name: _______________________________ _
Title: ------------------------------------
Address: -----------------------------------
Witness: ---=~------------------------------------Proprietorship or Partnership
Please indicate if one of the following applies:
Minority Owned/Controlled
Handicapped Owned/Controlled
Women Owned/Controlled
Submitted this ____ , day of ________ , 1996
RFP# 8
State of North Carolina
Department of Environment,
Health and Natural Resources
Division of Waste Management
James B. Hunt, Jr., Governor
Jonathan B. Howes, Secretary
William L. Meyer, Director
MEMORANDUM:
TO: Potential Respondents
November 5, 1996
From: Michael A. Kelly, Deputy Directo
Division of Waste Management
SUBJECT: REQUEST FOR PROPOSALS 0
.A.VA
DEHNR
The Division of Waste Management seeks proposals for testing of water, soil and
sediment samples from and around the PCB landfill in Warren County, North Carolina.
The scope of work is generally defined in the enclosed RFP which describes the samples
to be tested and methods to be to be utilized. The laboratory is to provide all containers and
shipping, and provide a cost estimate for personnel to be physically present to take custody of the
samples during the sampling event, estimated to take two days. The presence of laboratory
personnel is not a prerequisite to contract award.
All proposals are due to the Division of Waste Management by 12:00 noon, Friday,
November 22, 1996, Attention Michael A. Kelly, Deputy Director, 401 Oberlin Road, Suite 150,
Raleigh, NC 27605.
No pre-bid meeting will be held. Questions may be directed to Michael A. Kelly at 919-
733-4996, Extension 201. No further questions will be answered on this RFP after 12:00
noon on Wednesday, November 20, 1996.
P.O. Box 27687,
Raleigh, North Carolina 27611-7687
Voice 919-733-4996 ffffi:41/NMN
FAX [phone]
An Equal Opportunity Affirmative Action Employer
50% recycled/10% post-consumer paper
TRANSMISSION REPORT 1 1 r1 ~ 1 Q Q ~ ■ ~ b ■ J J b 1 -:r ■ c:-•71 ■..:• • ·-· .. _ 9197153605 SOLID WASTE DIU DATE T !ME [)URAT!Ot-l REMOTE I[) MO[)E PAGES RESULT 11.t1i;, 13:47 0 1 ·' 4 '3 ·'·' 861293:::2917 (:i 3 2 0. K.
PROPOSAL NO. PCBLF~ Issue Date: November 61 1996
NC DEPARTMENT OF ENVIRONMENT HEAL TH AND NATURAL RESOURCES
DIVISION OF WASTE MANAGEMENT
Request for Proposal
for
Testing for Dioxins/Furans
Closing Date: November 22, 1996 Time: 12:00 noon
Send all proposals directly to:
(if using U.S. Postal Service)
NC Department of Environment
Health and Natural Resources
Division of Waste Management
401 Oberlin Road, Suite 150
Raleigh, N.C. 27605
Attn: Michael A. Kelly
Please note the proposal number and closing date on the bottom left hand comer
of your return envelope.
PARTI
SOLICITATION INSTRUCTIONS
1.1 This request for proposals (hereinafter referred to as ("RFP") solicits
proposals for contractual services pursuant to Section 1 NCAC 5D.0300.0509
of North Carolina Administrative Code.
Mark outside of return envelope: Reply to PCB LF-3
1.2 Using Agency
The services solicited herein shall be performed for:
Department of Environment, Health , and Natural Resources, Division of
Waste Management
1.3 Issuing Agency
Department of Environment , Health, and Natural Resources
Division of Waste Management
401 Oberlin Road, Suite 150
Raleigh, NC 27605
(hereinafter referred to as DEHNR)
Attention: Michael A. Kelly
Telephone: [phone] ext. 201
1.4 Copies of this request for proposals will be distributed only by mail or they
can be obtained in person from Suite 150, 401 Oberlin Road, Raleigh, NC
27605.
1.5 Sealed proposals subject to the terms and conditions made a part hereof will
be received at the address specified in 1.3 until 12:00 noon December 2, 1996.
1.6 Refer technical inquiries to:
Michael A. Kelly
Division of Waste Management
401 Oberlin Road, Suite 150
Raleigh, NC 27605
Telephone: [phone] ext. 201
1.7 Pursuant to Article 3 and 3C, Chapter 143 of the North Carolina General
Statutes and Executive Order No. 34, the State invites and encourages
participation in this procurement by businesses owned by minorities,
women and the disabled including utilization as subcontractors to perform
functions under this Request for Proposals.
1.8 Performance and Default: The State reserves the right to require a
Performance Bond from the successful offerer as provided by law without
expense to the State. Otherwise, in case of default by the contractor, the
State may procure the services from other sources and hold the Contractor
responsible for any excess cost occasioned thereby.
1.9 The State reserves the right to accept or reject any and all proposals; to
waive any informality in proposals; and, unless otherwise specified by the
offerer, to accept any item in any proposal.
1.1 O Pricing: If either a unit price or an extended price is obviously in error and
the other is obviously correct, the incorrect price will be disregarded. The
right is reserved to accept other than the lowest priced proposal as may be
determined to serve the best interest of the State Agency.
1.11 Award: All qualified Proposals will be evaluated and acceptance made on
the Proposal judged by the Contracting Agency to constitute the best value
offered for the purpose intended. Evaluation will be based on contractor's
qualifications, experience, similar related experience, past performance,
financial standing, labor supply, hours offered, references, cost and overall
ability to perform the service required . The Contracting Agency reserves
the right to contract with more than one offerer to provide the services
described herein.
1.12 No Bid/Offer: Unless a response, in the form of either a proposal or a
written decline to offer a proposal, is received, offerer's name may be
removed from the applicabl~ mailing list.
1.13 Cost for Proposal Preparation: The State will not reimburse offerers for
costs incurred in the preparation and submission of proposal.
1.14 Offerer's Representative for Business Purpose: The name, mailing
address, and telephone number of the offerer's authorized agent with
authority to bind the firm and answer official questions concerning the
offerer's proposal must be clearly stated.
1.15 Time for Consideration: Preference may be given to proposals allowing
not less than 30 days for consideration and acceptance.
1.16 Telegraphic Offers: Telegraphic and telecopy offers will not be
considered; however, offers may be modified by such means, providing
such notice is received prior to the date and time of bid opening above
specified, and provided a signed original follows.
1.17 Any explanation desired by an offerer regarding the meaning or
interpretation of the RFP, attachments, specifications, etc. must be
requested in writing and with sufficient time allowed for a reply to reach
offerers before the submission of their offer. Oral explanation of
instructions given before the award of the contract will not be binding. Any
information given to a prospective offerer concerning the RFP will be
furnished to all prospective offerers as an amendment to RFP. if such
information is necessary to offerors in submitting offers on the RFP or if
the lack of such information would be prejudicial to uninformed offerers.
1.17 .1 Acknowledgement of Amendments to RFP: Receipt by an
offerer of an amendment to this RFP must be acknowledged
by including a copy with offeror's proposal.
. 1.18 The successful bidder shall provide adequate facilities, labor, equipment,
services, supervision and lay days to meet all conditions of the contract
specffications. :
1.19 The successful bidder covenant~ and agrees to save ha:mless the State
from any expense, loss or damage to the contractor's equipment, facilities
or property or any claim or cause of action which may arise as the result
of the performance of the work specified in the contract.
1.20 Each offerer is cautioned that the State is not obligated to ask for or
accept, after the closing date for the receipt of proposals, data which is
essential for a complete and thorough evaluation of the proposals. The
State of North Carolina may award a contract based on initial offers
received without discussion of such offers. Accordingly, each initial offer
should be submitted on .the most favorable and complete price and
technical terms which the offerer can submit to the State.
1.21 All proposals, after the award of the contract, will be open for public
inspection. Trade secrets, test data and similar proprietary information will
remain confidential provided such material is clearly so marked when
submitted. However, net cost information cannot be confidential.
Part II
2.0 Background on Warren County PCB Landfill
2.0.1 The State ofNorth Carolina (State) owns and maintains a closed (July 1983)
polychlorinated biphenyl (PCB) chemical waste landfill permitted in accordance
with the Toxic substance Control Act (TSCA) and 40 CFR Part 761.
2.0.2 The PCB landfill is located on the East side of SR 1604 approximately 1.5 to
2 miles from the intersection of SR 1604 and US 401 South, 2-3 miles
from Warrenton, North Carolina.
2.0.3 The State has established a Joint Warren County/State PCB Landfill
Working Group (Working Group) to evaluate technologies and tasks associated
with the detoxification of the landfill. The Working Group has hired two Science
Advisors to work with the Group and the State and any other entity through this
project.
2.0.4 The purpose of this RFP is to solicit laboratories interested in providing dioxin/
furan testing on a variety of samples to be taken from and around the landfill,
and, at the discretion of the Working Group, be prepared to provide an individual
to be on hand for the sampling event and to take custody of the samples at the
landfill.
2.1 Concept of the operation
2.1.1 Members of the Division of Waste Management, with the Science Advisor's,
will be responsible for taking all samples at the site. It is currently estimated
that the sampling event will require two days, and hopefully take place within the
next 45-60 days.
2.12 One of the Science Advisors will assign the codes to all samples and maintain the
master roster. A draft sampling plan has been completed and will be made
available to the contractor for the dioxin/furan analysis.
2.1.3 Each prospective bidder should include a separate cost estimate for
providing one or two staff members on site to take custody of the samples and
ship to the laboratory. If this is not possible as a result of lab location or
availability of personnel, please note on the bid. Ability to comply with 2.1.3 is
not an absolute in order to be awarded the contract.
2.1.4 It is estimated that there will be a minimum of 40 and a maximum of 50 samples
within the following categories and current estimates:
Well water Estimate 18
Leachate Estimate 02
Surface water Estimate 06
Sediment Estimate 04
Soils Estimate 06
Filter bed Estimate 02
Blanks Estimate 06
The laboratory will be responsible for providing appropriate containers for all
samples and to pay shipping costs. The state reserves the right to add more
samples to this contract or to change the numbers in the respective categories.
2.1.5 All analytical work will follow the Method 8290, full Tetra-octa scans and a Level
III Report summary package for the samples and calibration raw data. An
example of the reporting format should be included in the bid package. All
results are to also be reported in a table format showing sample numbers and
results as a single dioxin number.
2.1.6 Each bid package should indicate what the standard turn around time is for sample
results, as well as include a specific matrix for costs associated with quick turn
around in 7 and 14 days.
2.2 Deliverables
() Vt"\ {Jo ~M-1
2.2.1 Bi~should include the following:
-Unit price per sample
-Turn around time, cost to expedite
-Sample report
-Cost to mobilize 1-2 individuals to receive samples at the landfill
-Overnight shipping charges for samples
-Cost for sample containers, if charged separately
-Other-any other items which may need to be considered in the cost estimate
-List of 5 references
-Required prior notification for start-up of work.
2.3 Criteria for selection of respondent
2.3 .1 Demonstrated experience and qualifications in dioxin/furan testing
2.3.2 Cost ·
2.3.3 Past performance with respect to working relationships with clients
2.3 .4 Capabilities
2.3.5 Capability and commitment to work with the Department and citizens of
the Working Group.
2.4 Process for selection
2.4.1 RFP is being sent to six laboratories across the country that have the capability
to provide this type of testing.
2.4.2 No pre-bid conference will be held. Questions may be addressed to Michael A.
Kelly, Deputy Director, DWM, at 919-733-4996, extension 201. No further
questions will be answered after 12:00 noon on Wednesday, November 20, 1996.
2.4.3 A bid response date of 12:00 noon, Friday, November 22 has been set. All
Proposals must be received by this time and date, attention Michael A. Kelly,
Deputy Director, Division of Waste Management, 401 Oberlin Road, Suite 150,
Raleigh, NC 27605.
2.4.4 All respondents submittals will be reviewed and a selection of at least 3 proposals
will be presented to the Working Group and Science Advisors who will make a
recommendation to the Department for final selection of the contractor.
2.4.5 All respondents should indicate their necessary lead time for work performance
once contract is awarded.
2.5 Attachments
2.5.1 Location/vicinity maps
2.5.2 Monitoring well location and map oflandfill.
Final revision November 6, 1996
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State of North Carolina
Department of Environment,
Health and Natural Resources
Division of Solid Waste Management
James B. Hunt, Jr., Governor
Jonathan B. Howes, Secretary
William L. Meyer, Director
MEMORANDUM
a a
DEHNR
October 29, 1996
To:
From:
Dr. Mike Moser, Director Division of Epidemiology
BillMeye~
Subject: Dioxin cleanup levels -PCB landfill detoxification
Enclosed is a draft document on cleanup levels for dioxin contaminated soils. The Joint
Warren County State PCB landfill Working Group (Working Group) will be involved, along with
their science advisors, in making a recommendation for cleanup levels in the landfill. Dr. Joel
Hirschhorn is one of the science advisors. It is assumed that Dr. Hirschhorn will propose cleanup
levels consistent with the enclosed draft document. Please note also the potential for changes in TEQ
when both PCBs and dioxins are considered in combination (synergistic effect(s)).
The Division would appreciate your review of the document and also consider working with
Dr. Hischhorn and the Working Group during efforts to consider cleanup objectives for the PCB
landfill detoxification.
cc: JoelHischhorn
P.O. Box 27687,
Raleigh, North Carolina 27611-7687
Voice 919-733-4996
FAX [phone]
An Equal Opportunity Affirmative Action Employer
50% recycled/10% post-consumer paper
c:LEANIJP .:LEVELS ro:R
:n:1ox1N
CONTAMINATED SOILS
Joel S. Hirschhorn
Hirschhorn & Associates
2401 Blueridge Ave., Suite 411
Wheato~ MD 20902
_ [phone]
FAX [phone]
August 1996
This paper is being submitted for publication
in a leading peer reviewed environmental journal.
Abstract
CLEANUP LEVELS FOR DIOXIN CONTAMINATED SOILS
JoelS. Hirschhorn
Hirschhorn & Associates
2401 Blueridge Ave., Suite 411
Wheaton, MD 20902
EPA's use of a 1 part per billion level for dioxin contamination in residential soils is shown
to be too high and not protective of public health. It was derived in a 1984 cancer risk assessment
by another federal agency, but it is inconsistent with risk-based levels of2 to 4 parts per trillion
obtained by using EPA's risk assessment methods. EPA has called the 1 ppb level a policy-based
levei which correctly distinguishes it from a risk or health-based cleanup standard. Tue 1984
assessment is shown to have shortcomings, and its policy recommendation of using 1 ppb was not
consistent with its scientific conclusions and caveats. For over a decade dioxins have been left in
soils at levels posing health risks and sometimes that EPA is legally required to address.
Moreover, noncancer effects have been ignored, but recent work has shown them to support
action at levels much lower than 1 ppb. To protect public health and be consistent with current
scientific knowledge and other EPA policies new EPA policy guidance for dioxin soil cleanups is
needed, and key elements are presented.
Key words: dioxin, risk assessment, soil cleanup, Superfund
Jntroduction
For soil cleanup decisions at Superfund sites, EPA has used 1 ppb of dioxin contamination
for over a decade. At issue is whether this level is protective of public health. Although given
originally as the concentration of the most toxic dioxin isomer, it now is given as toxic equivalent
(TEQ) concentration. TEQs are obtained from using toxic equivalency factors (TEFs) for ce1tain
dioxins and furans that convert or normalize concentrations to equivalents for the toxicity of
2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), which has a TEF of one.
Surprisingly, even though there has been remarkable attention to and publications on
dioxins, there has been no detailed examination of the widely used 1 ppb cleanup level. This
analysis provides new information about the scientific basis for the 1 ppb levei alternative values
obtained by using EPA's methods, new information from the Agency for Toxic Substances and
Disease Registry (ATSDR), and information on EPA's use of 1 ppb in the Superfund program
and how its use compares to other EPA policies.
1
Source of the 1 ppb value
A paper published in 1984 by Centers for Disease Control (CDC) staff presented th.is-
value, 1 although the figure had probably. been disseminated within government in 1983. CDC
performed a cancer risk assessment that was based on doses for 10-6 risk, and exposure doses for
residential exposure to contaminated soil. CDC said that 1 ppb was "a reasonable level at which
to begin consideration of action to limit human exposure for contaminated soil."
For Superfund decisions, a 1989 EPA memo has been cited by EPA as setting a policy of
using the 1 ppb figure as an action or health concern level.2 Tue memo cited the CDC paper as
the source of the 1 ppb figure. Tue memo was for a particular Superfund site decision and was
not issued as EPA policy guidance. Importantly, the memo noted ''that 1 ppb does not represent
a fine line between safe and unsafe conditions as the term 'action level' implies." But it has been
used in exactly that way. The memo did not include EPA's 1985 health assessment for dioxins3
among the references it cited. EPA still uses the cancer potency obtained in its 1985 study.
In 1987 EPA released the results ofits National Dioxin Study,4 which included soil
contamination data for some Superfund sites, but the laboratory testing detection limit was only 1
ppb for about 75% of the sites, meaning that levels below that were largely unaccounted for, as if
they were unimportant. If dioxin TEQ levels below 1 ppb are of health significance, then rather
than using EPA's method 8280 for dioxin testing which has a generic detection limit of 1 ppb,
only method 8290 with one of 1 ppt is appropriate. Tue continued use of 1 ppb as a cleanup
standard has sometimes resulted in the less accurate laboratory method being used, leading to
unreliable data for lower dioxin levels.
EPA risk assessment
EPA has developed risk assessment procedures and established presumptive numerical
values for key parameters. EPA Region 3 issues a widely used set of risk-based concentrations,
based on 10-6 risk, including values for residential soil ingestion. 5 Its value for TCDD is 4 ppt.
Changes in the parameters used in risk calculations can change this value, even for what
seems as the same basic residential exposure and risk level. For example, an EPA contractor for
the Escambia Treating Company Superfund site, Pensacola, Florida, calculated a soil level of 2
ppt TEQ for residential exposure and 10-6 risk. This figure reflected three exposure pathways of
ingestion, inhalation, and dermal exposure, that was appropriate because soil in an adjacent
community had been contaminated by dioxin for many years. EPA's 4 ppt is for ingestion only
and is more appropriate for soils on a cleanup site. The state of Georgia publishes a value
corresponding to 4.8 ppt, following EPA risk methods, but probably with some minor change in
one or more parameters.
Another issue is exposure to other site contaminants, especially PCBs, because they are
related to dioxins in molecular structure and toxicity, but EPA has not yet determined TEFs for
2
them EPA has said that PCBs could double or triple TEQ values, and a leading dioxin expert has
said that dioxin TEQs should be doubled to account for contributions by PCBs. 6 Recent research
supports this view of PCBs.7
Difference between EPA and CDC soil levels
All risk assessments use the same basic method. But they can and are used and presented
in different ways. EPA' s value of 4 ppt was obtained by asking the question: what level of dioxin
contamination in soil corresponds to a I o-6 cancer risk, assuming various parameters for ingestion
from residential exposure? But CDC asked: assuming a level of I ppb TCDD in soil and various
exposure parameters, is this level of health concern? There are two basic components of risk
assessment: (1) determining an uptake dose from the contaminated soil, and (2) determining a 10-6
risk-based dose from toxicity data. EPA used one set of toxicity data, while CDC used that one
plus another. CDC used a range of 10-6 doses (.028 to 1.428 pg/kg-day), and the low dose came
from the toxicity data also used by EPA, but the highest doses came from the other data. The
dose range allowed a risk range to be calculated. The lowest cancer dose equated to a risk of 2. 3
x I 0-5 for I ppb dioxin contamination and various exposure assumptions.
However, the lower limit dose does not correspond to the value obtained in 1985 by EPA
and still used, which was .006 pg/kg-day. This smaller dose resulted from use of a higher toxicity
or cancer potency than most of the data used by CDC. This lower EPAdose, together with
CDC's exposure assumptions, results in a risk of 1.1 x 10-4 for I ppb dioxin.
CDC's exposure model used assumptions to obtain uptake dose that merit attention. For
example, it assumed that _the I ppb level might be in I 00%, I 0% or I% of soil, and that some soil
had no dioxin contamination. This is like assuming that I ppb is a maximum value, but not
necessarily the average level over an area. EPA data are normally average levels. CDC assumed
a 12 year half-life for TCDD in soil, meaning that exposure over decades would not be to the
initial level, but to much lower levels. Remarkably, the same CDC paper also said that "The half-
life of TCDD in soil is not known." A brief discussion noted the degradation by ultraviolet light
required certain chemical circumstances, and that biodegradation would occur "at a very slow
rate." Although there is no consensus on soil half-life for dioxins, the best estimate is 25 to I 00
years.8 CDC's assumptions lowered uptake dose and health risk.
CDC used higher ingestion rates of soil for children than EPA does, but the level for
adults was the same. Various assumptions were used for dermal and inhalation uptakes, not all of
which agree with EPA values. The overall impact of all CDC's assumptions was determined.
EPA's smaller 10-6 dose was used while maintaining the other parameters the same as CDC used.
The result is 9.4 ppt for TCDD in soil. Because this is greater than the 2 ppt obtained for a
similar multipath exposure by using EPA's procedures, all of CDC's data reduced total exposure
and dose, and therefore risk, as compared to EPA's method.
CDC concluded: "the excess lifetime cancer risk for exposure to residential soil with a
3
peak TCDD contamination level of 1 ppb ranges over 4 orders of magnitude, from above 10-5 to
below 10-8." Over time, EPA and others have ignored CDC's risk range for 1 ppb and, especially,
that risks lower than 10-5 resulted from a cancer potency lower than that used by EPA and less
conservative exposure assumptions. If EPA's cancer potency and exposure assumptions are used,
an average concentration of 1 ppb has a risk of 5 x 1 o-4, which is high. The 1 ppb level is not a
1 o-6 risk based concentration. It is a value that CDC associated with a range of 1 o-6 risk cancer
doses, all greater than EPA's value, and exposure conditions that in total resulted in less dioxin
uptake than with EPA's exposure parameters.
CDC's policy recommendation
The CDC statement that 1 ppb "is a reasonable level at which to begin consideration of
action to limit human exposure for contaminated soil" was given in the paper's abstract. But in
the paper's summary, CDC said ''we have concluded that residential soil levels greater than 1 ppb
TCDD pose a level of concern." These are two very different statements. The second one was a
clear scientific conclusion that is compatible with EPA's value of 4 ppt, because it did not specify
a safe-unsafe boundary, but only an unsafe level. The abstract's statement was a policy
recommendation for government to use a 1 ppb level to decide whether or not to take action,
such as soil cleanup or relocation of residents, that EPA adopted. As the above analysis has
shown, the policy statement is inconsistent with EPA's scientific findings and risk assessment
procedures, is not fully supported by CDC's findings, and has resulted in the incorrect belief or
assertion that levels below 1 ppb are not of health concern.
The CDC paper had other related statements, including "a soil level of I ppb TCDD in
residential areas is a reasonable level at which to express concern about health risks." ( emphasis
added) This phrase is not equal to the policy recommendation of "at which to begin consideration
of action." Another CDC statement was "Although from these calculations levels of TCDD
below 1 ppb are, for practical purposes, considered not to reach a level of concern, several
additional considerations related to the risk assessment calculations should be pointed out to
decision-makers involved in risk management." In fact, the paper had several critical caveats,
such as acknowledging "insufficient information about exposure of people to soil, and insufficient
information about intake ofTCDD by humans from such soil." Also, ''whether a certain level of
TCDD in soil will give rise to concern has to be evaluated on a case-by-case basis." No such
caveats accompanied the abstract's policy recommendation. Nor did they support use of 1 ppb as
a presumptive cleanup standard.
The CDC study had been conducted because of the highly publicized dioxin contaminated
sites in Missouri that EPA's Superfund program was addressing in a highly politicized
atmosphere. CDC was charged with determining ''what level represented an unacceptable risk to
the population living in these contaminated areas. "1 However, before the CDC risk assessment, at
the end of 1982, CDC had already issued a warning that Times Beach should be completely
evacuated on the basis of soil contamination data. In other words, CDC was asked to do what
ATSDR was subsequently created for. If CDC had said that contamination levels below 1 ppb
4
posed a health concern, EPA's decisions on soil cleanup would have been greatly affected, and
costs would have been much higher.
There would not have been an impact on relocation, because EPA had decided in early
1983 to buyout all residents that had been supported by the CDC warning several months earlier.
The Missouri buyout was seen as an attempt by EPA to "reverse the agency's tarnished image,"9
because at the time EPA was in turmoil, under intense public scrutiny, and top political appointees
were dismissed or resigned. Later, attention shifted to soil cleanup. In 1986, Syntex attempted to
get EPA to increase the soil cleanup level from 1 ppb to 10 ppb to save 65% of cleanup costs that
it and other companies were responsible for. 5 In fact, the uncertainties and caveats in the CDC
paper could be used to support such an effort, making 1 ppb seem like a political compromise.
EPA's desire to have companies pay for Superfund cleanups has conflicted with reducing the
dioxin cleanup level below the CDC figure. In 1988 EPA used the I ppb level in its decision for
Superfund cleanup at Times Beach, Missouri. It set the stage for EPA's dioxin soil cleanup level
becoming policy-based rather risk or health-based.
Noncancer health effects
A recent paper by ATSDR staff addressed noncancer health effects and possible levels of
dioxins for cleanup decisions. '0 This is important, because over the past few years there has been
increasing recognition that noncancer health effects of dioxins may be more important than cancer
impacts. For example, a recent successful environmental book said "dioxin acts like a powerful
and persistent honnone that is capable of producing lasting effects at very low doses -doses
similar to levels found in the human population .... Dioxin and dioxinlike PCBs are known to affect
the immune system as well as many parts of the endocrine system."11 The ATSDR authors noted
that "recent studies suggest that non cancer end points may be more sensitive indicators of dioxin
exposure," and derived a value of 40 ppt for chronic exposure of children, which is called an
EMEG, or environmental media evaluation guide by ATSDR. EPA has also used a childhood
only basis for noncarcinogenic soil contaminants. 12
The authors also concluded that: ''No absolutely safe exposure (i.e., above zero) can be
identified." The cancer dose-response models used by EPA and CDC (i.e., linear multistage) also
assume that even one molecule can result in cancer.13 Although a recent analysis, using EPA's
dioxin toxicity data, showed only a 10·15 cancer risk from one TCDD molecule, 14 public concerns
about dioxin exposure are increasing, in large measure because of noncancer effects.
Moreover, the ATSDR authors acknowledged the need to address incremental exposures,
resulting from multiple, background, and past sources of dioxin exposures. They noted that
"ingestion of homegrown vegetables and fiuit, and dermal/dust inhalation exposure of those
working in the garden must be considered" and that "special attention must be paid to the
exposure of children playing on contaminated soil." In other words, depending on varying
background exposures for different people in different locations, an additional exposure from a
cleanup site may be more or less important in causing new or additional health effects. Also,
5
there has been recent findings of synergistic estrogenic effects among PCBs and pesticides which
strongly suggest similar interactions with dioxins. 15 All such conditions "suggest the need to
further lower the TCDD levels in soil in order to lower the total exposure," according to the
ATSDR authors. They recommended that although the 1 ppb level "may be appropriate guidance
value ... to the extent that parameters of exposure and/or human factors would suggest the
existence of at risk or vulnerable population groups, alternative values such as these outlined in
this paper should be considered."
The 1995 ATSDR Public Health Assessment for the Escambia site used an EMEG of 50
ppt for dioxin TEQ in soil. But ATSDR said "The levels of dioxin-TEQ in off-site soil are
unlikely to cause noncarcinogenic health effects." even though the report gave the maximum level
of950 ppt from 1992 testing. The report also said ''Because the cancer risk in people from
exposure to dioxin-TEQ is currently under scientific review, we do not know what carcinogenic
health effects are likely." But the uncompleted EPA dioxin reassessment did not nullify the EPA
cancer risk information that EPA itself has continued to use, including for the Escambia site. The
50 ppt value was ignored by EPA, which only focused on cancer risks and the 1 ppb level. This
author knows of no Superfund site where EPA has used noncancer effects of dioxin to set or
influence cleanup levels or other actions, such as relocation of residents.
Background levels and incremental risks
There is a critical need at Superfund sites to determine the local background level of
dioxins in soils and the level of dioxins in blood lipids in people plausibly exposed to site dioxins,
especially when contamination is fow1d in residential soils. Background data serve two purposes.
One is to decide whether soil contamination is significant. The other to determine whether an
exposed population has prior or multiple exposures. There is no scientific support for dismissing
dioxin contamination below I ppb as merely background concentrations, an approach often used
by EPA, unless data are obtained from control samples at some distance from the site. Using data
from locations near a cleanup site or on it, which is sometimes done, provide overly high levels
that are not true background levels. Higher than normal background soil and blood levels for an
exposed population provide the basis for lower dioxin cleanup levels, either on the Superfund site
or offsite, or both.
Background soil levels of dioxins in North America vary widely, from 2.26 to 13.66 ppt
TEQ, according to EPA.16 This range is not surprising, because some geographical areas, even at
significant distances from point sources, have been impacted by air deposition of dioxin
contaminated particles from waste incineration, industrial manufacturing, and other sources.
Also, EPA assumed nondetects equal to half the detection limit, which is EPA's procedure for
risk assessment, 17 but is not necessarily used when data are reported. A study on dioxin
background exposures in the United States assumed only a . 96 ppt TCDD soil level, compared to
EPA's average of 8 ppt TEQ.
The background level issue and paying attention to multiple exposures to dioxin were
6
examined in a 1985 EPA analysis that focused on findings of dioxin soil contamination in
Midland, Michigan, where Dow Chemical operated a plant that had produced pesticide chemicals
having dioxin contamination and incinerated chemical wastes.18 The EPA risk assessor argued
that 1 ppb was probably not appropriate to evaluate the findings. EPA's data showed the average
level ofTCDD (TEFs were not set until 1989) to be 48 ppt in Midland residential and public
access soils, as compared to 2.4 ppt in Middleton, Ohio, a comparable industrial city. The
average level around the perimeter of the Dow Chemical plant was 327 ppt, compared to 2.2 ppt
around a steel mill in Middleton. Dow Chemical had obtained its own data on soil levels in a
number of industrial cities and reported an average of 2.2 ppt. The EPA risk assessor argued that
the Midland levels were not normal background levels, and were especially significant because
many residents had been exposed as workers at the Dow Chemical plant, that people had been
exposed to soil and air dioxins for decades because of release from the facility, and that they had
eaten homegrown vegetables and fish from a local river that were probably contaminated by
dioxins.
Here was a specific case where site specific circumstances showed the need to see levels
below 1 ppb as of health concern, and to use a lower level for cleanup and relocation decisions.
Like the Missouri situation, here too there was a political dimension, because in early 1983 tQere
was a controversy involving a senior EPA officiaL forced to resign, based in part on actions that
allowed Dow Chemical to affect EPA's decisions on dioxin contamination in Michigan.8 It is
clear that the Missouri and Midland cases were the precedents for EPA's rise of the 1 ppb level as
a policy-based figure.
EPA's actions for the Escambia site in Pensacola also illustrate problems related to
background levels. In 1995 soil sampling was done in the residential community close to the
Escambia site, part of which is adjacent to the Escambia site and part a little more distant and
even closer to another Superund site (Agrico Chemical). Samples were also taken from four
areas outside this immediate community but only slightly further away. EPA has acknowledged
levels of dioxin contamination of health concern only in a small portion adjacent to the Escambia
site, where the average level was 587 ppt TEQ, but where several locations had levels above 1
ppb. 1l1e area a little further away from the Escambia site had an average of 70 ppt, and the next
more distance area 7.3 ppt. In the neighborhood closer to the other Superfund site, that is more
distant from the Escambia site, the aver~ge was 12.4 ppt. For the four areas outside the
residential community, a school yard had 7 ppt, a baseball field 7.5 ppt, a vacant lot 22. 7 ppt, and
a residential yard 7.8 ppt.
EPA's position was that all the areas, except the one adjacent to the Escambia site (where
the I ppb level was exceeded) did not pose health risks and that they had not been impacted by
the Escambia site. No data were obtained, however, to determine background levels in the
Pensacola area. Nearly all dioxin levels were above the 2 ppt determined for residential exposure
and 10·6 risk, including two areas where children spent time (the baseball field and school). It
should also be noted that some residents were exposed as workers at the former Escabia
operation, that the dioxin contamination of the residential soil had initially occurred many years
7
before the site entered the Superfund program, that an EPA removal action that excavated an
enormous amount of contaminated soil and piled it on the site had probably caused some releases
of dioxin, that soils were contaminated by several other highly toxic chemicals, and there were
pervasive health problems in the community. Thus, the issue of incremental dioxin risk was
relevant as evidenced by an ATSDR Health Consultation for the Escambia site prepared in 1992
and its review by the ATSDR Health Activities Recommendation Panel. Because of"likely"
worker exposures at the operating wood treating company and because "off-site exposures may
have occurred," the panel recommended a health evaluation ofresidents living the site. It was to
include physical examinations and laboratory tests. These were not implemented, however. The
testing for dioxin in blood lipids would have provided important data regarding past exposures to
dioxin among residents.
A recent study revealed the proper use of offsite control soil samples to obtain
background levels. 19 Interestingly, the average background TEQ level was higher than the
cleanup site's level, and both were very low (less than 3 ppt). The background levels were
explained as resulting from the impacts of traffic on a major highway on an otherwise rnral area.
The data supported the conclusion that the cleanup site was not contaminated by dioxins.
Prospective versus retrospective exposures
Dioxin risk assessment work has focused on prospective residential exposures and
whether residual soil levels after cleanup would pose unacceptable health risks. Oddly, however,
in many cases dioxin contamination is found in residential soils where people have already been
exposed to the levels found. While the prospective approach is valid for cleanup sites themselves,
that might become residential areas, the retrospective approach accounts for additional
incremental dioxin risk for dioxin contaminated residential areas with exposed populations.
CDC's work for Missouri was such a situation, yet its analysis was only prospective.
Instead of using a half-life to calculate lower dioxin levels for future exposures, it should have
worked backwards to obtain higher levels for the people exposed to the soil in the past. As in the
Missouri, Midland, and Pensacola cases, for many situations the retrospective approach is
necessary, and even EPA's levels of 2 to 4 ppt are not necessarily protective when additional
incremental dioxin risk is considered. .
Consistency with cleanup levels for other site contaminants
At most Superfund sites, soil contaminants are designated as Contaminants of Concern,
and EPA sets cleanup levels as preliminary or final remediation goals. In many cases, these are
based on 10-6 risk and residential exposure. In those cases, when dioxins are also site
contaminants, the issue arises as how EPA can use I ppb when according to EPA's own risk
numbers the 1 o-6 risk is 2 to 4 ppt. Reasonable people question how the government can use the
l o-6 risk level for every toxic chemical except dioxin, that EPA acknowledges to be the most toxic
chemical. Moreover, if some soil with up to 1 ppb dioxin remains after cleanup, then residual
8
risks are I 0·4, negating the benefit of cleaning up the other contaminants to I o-6 risk levels.
EPA soil screening values
EPA has established generic soil screening levels for 110 chemicals, for use in the
Superfund program 10 These are based on 1 o-6 risk and residential soil ingestion exposure. They
can serve as preliminary or final remediation goals, unless site specific information is used to
support other levels. But no value was presented for dioxin. The explanation from EPA is that a
policy decision had already selected 1 ppb, and that EPA's dioxin reassessment is ongoing.
EPA 's use of the 1 ppb level
A good example of the current problem is an EPA study in 1995 that tested residential
area surface soils in a small town, Tifton, Georgia, with a number of toxic waste sites. EPA
dismissed the findings of dioxin in all 14 samples solely on the basis that they were below 1 ppb. 20
This author's analysis of the data foWld that the sample locations could be divided into tluee
groups, based on distance away from the Marzone/Chevron Superfund site. 1t was found that the
5 residential soil samples closest to the site (about a quarter mile or less) had au average dioxin
TEQ level of 65 .2 ppt ( with a maximum of 120 ppt ). For the three locations further away the
average was 5.9 ppt. For the 6 locations about one-half to a mile away the average was 2.6 ppt.
However, the detection limits were uuusually high for the 8290 method, _.suggesting systematic
underestimates ofTEQ dioxin. TI1is was compounded by the procedure of ignoring all
nondetects. EPA guidance is to use onehalf the detection limit. Correcting the data resulted in
TEQs for the three zones given above of 66.8, 14.4 and 10.5 ppt, with increasing distance from
the Superfund site. lltis _is strong evidence that dioxins had migrated from the site into the
surrounding community by means of airborne transport of dioxin contaminated soil pa1ticles (from
the cleanup site or from the original industrial operation at that site). The corrected TEQs,
moreover, indicate levels of health concern at all distances from the cleanup site.
Although ATSDR reviewed the data for EPA, it simply said that the levels found were
below health concern, without providing any explanation or analysis, and ignored the EMEG of
40 ppt for noncancer effects, exceeded at three locations near the site. No problems with the data
were noted. Neither EPA or ATSDR noted, at the time the study report was released, that no
testing of dioxins had ever taken place at the two toxic waste sites fitting categories known to
likely have dioxin contamination (pesticide and wood treating sites).
Subsequently, when testing showed widespread dioxin contamination at the
Marzone/Chevron site, where EPA had previously established pesticide cleanup levels for 10·6 risk
from residential exposure, EPA attempted to dismiss all findings below 1 ppb, choosing to focus
on one area with levels well above 1 ppb (maximum of 3 ppb ). For these test results onehalf
detection limits were used for nondetects. The position that dioxin contamination in the main
former pesticide factory surface soil was just backgroW1d, and not a result of pesticides, was
inconsistent with the average level of 45 ppt TEQ (maximum of 276 ppt), findings of dioxin in
9
subsurface soil (greater than surface soil levels) and chemical storage tank contents, and the lack
of measuring background TEQ in the Tifton area. Where subsurface dioxin levels were
substantially greater than in surface soils, levels of site pesticides were also correspondingly
greater than in surface soils, providing additional support for concluding that dioxin
contamination was caused by some pesticides handled at the site.
In 1996, EPA Region 4 conducted an analysis of dioxin cleanup levels at Superfund sites
(unpublished). Over 12 years, 20 sites used the 1 ppb leve~ and 6 used levels greater than I ppb
and 7 less than it. In tluee cases the cleanup levels were low, between 4 to 7 ppt, at about the
1 o·6 risk level. Nevertheless, EPA officials often state that it would set a dangerous precedent if a
value less than 1 ppb was used. The "danger" is economic, namely that a lower cleanup or action
level increases the costs of cleanups and relocations, and might affect decisions already made and
cause more cleanup. New residential areas built on soil previously cleaned up to 1 ppb would be
vulnerable.
Legally, it is clear that the 1 ppb value is, at best, only guidance, but it was never issued by
EPA as guidance. At various times EPA has stated that the 1 ppb level is an action level, a
screening ]eve~ and a level of health concern. It is not, however, a rigid cleanup standard having
statutory or regulatory standing. Yet as concerns about Superfund costs, funding and liabilities
have increased, EPA's desire to impose the 1 ppb level has increased. The 1989 EPA memo had
cited the important caveats of the 1984 CDC paper about making decisio~1s on the basis of site
specific circumstances. A 1992 EPA memo on the strategy to be used in the Superfuud program
for addressing information from the agency's dioxin reassessment made no mention of the
program's use of 1 ppb.21 Ways in which decisions could be reopened were presented and a
commitment was made to ''use the best science available in making its decisions." But the proper
policy statements by EPA have not resulted in retrenchment from EPA's use of 1 ppb as the
presumptive dioxin cleanup standard. Only a few Superfund site decisions have used lower levels,
and they were not major sites.
Data on other types of cleanup sites, federal and state, are difficult to obtain. But a
cleanup at the Naval Seabees Center, Gulf.point, Mississippi, used a dioxin cleanup level of 5 ppt
to remove contaminated soil with about 100 ppt dioxins. And the state of Florida is using a 7 ppt
level for a 10·6 risk and asking that it b~ used for the cleanup of the Coleman-Evans Wood
Preserving Superfund site. If a state has some type of standard, requirement or criterion for a
lower dioxin cleanup level, than EPA can be compelled by statute to use it.
Legal violation
The 1 ppb level corresponds to a risk over 10·4 according to EPA's risk data. Under the
federal National Contingency Plan (NCP) governing the Superfund program, such risks require
EPA action. There is some confusion over what current risk requires EPA action versusfuture
risk and cleanup goals, because of the NCP's risk range of 10·4 to 10·6. But NCP language, EPA
guidance, and recent General Accounting Office reports made it clear that current risks above I 0·4
require EPA action,22 usually by taking a removal or emergency action, or an interim remedial
action. EPA does not have to achieve future residual risks of J o-6, but under the NCP if it does
not it must explain why. Usually, the reason is non-residential exposure. Using EPA's figure of 4
ppt, 10-4 risk equates to a soil level of 400 ppt (appropriate for cleanup site soils), and using 2 ppt
it is 200 ppt ( appropriate for residential soils). In other words, when data reveal levels above
these, EPA is legally required to take action. Conversely, when EPA ignores levels below 1 ppb
and above these lower levels, it is not complying with the NCP.
At the Escambia, Pensacola site in 1992, after EPA had completed a removal action that
consisted of a massive excavation of contaminated soil to protect groundwater, it tested soil in a
few residential backyards immediately over the site's fenceline and found dioxin, ranging from 34
to 950 ppt TEQ with an average of 316 ppt. It used a sample for background very near these
locations and on the Escambia site itself that had 14 ppt. Three years later, EPA obtained more
dioxin data showing even higher levels in residential soils (average of 587 ppt TEQ and maximum
of 3 ppb in the area closest to the site). Four years after the original evidence of dioxin
contamination in the residential area, EPA had not taken any action, such as soil removal, soil
covering, or relocation of residents to protect public health against risks greater than J 0-4
_ The
residents were not helped by ATSDR's Public Health Assessment in 1995 that raised no concerns
about dioxin.
Treatment technology
It is also relevant that in 1994 EPA established universal treatment standards as part of its
land disposal restrictions program under the 1984 Hazardous and Solid Waste Amendments. The
treatment standard for TCDD is 1 ppb, which apparently was taken from the policy-based level of
I ppb for cleanups. This ~tandard can be applied to technologies used to detoxify dioxin
contaminated soil. It provides a disincentive for achieving lower levels. It also suggests problems
because ofland disposal of soils with dioxins at lower concentrations that pose health threats.
EPA's original concerns in the 1980s about cleanup costs, especially if treatment
technology such as incineration was used, are less warranted today. There are more technologies
than ever, including BCD dechlorination developed by EPA and licensed to several companies
that have commercialized it, a Canadian technology that destroys dioxins, and several commercial
solvent separation technologies. 23 It is possible to achieve residual levels to low ppt levels.
Increasing competition has reduced unit costs. People concerned about dioxin exposure have
learned about these newer technologies.
Dioxin cleanup and risk management policy
Since the mid-l 980s EPA has used an increasingly inconsistent and technically indefensible
basis for decisions about dioxin contaminated soil. The 1 ppb level was based on a risk
assessment by CDC that had deficiencies and to some extent misrepresented its results to present
a simple policy decision rule with enormous economic implications. There was considerable
11
demand for that dioxin cleanup level in the mid-1980s. Now, however, there is no credible
scientific, health based, or logical defense for using the 1 ppb figure. The translation of CDC's
risk assessment results into a Superfund action level and EPA's initial uses of it occurred during
the aftermath of the 1983 backlash against the environmental policies of the Reagan
Administration. But many senior EPA managers still believed in those policies, and they
established a policy-based dioxin cleanup standard that has prevailed.
Changing to a scientifically credible health-based dioxin cleanup level has been seen by
subsequent EPA managers as threatening. Rather than focusing on health risks, they manage
bureaucratic risks. Lower dioxin soil cleanup levels could result in demands to reopen past
cleanup decisions that in combination with more stringent cleanup decisions would require higher
federal appropriations for the Superfund program at a time when they are being decreased. Yet
this problem only worsens with time as more decisions are based on 1 ppb. Concerns about
cleanup costs are valid, especially by government officials, but using 1 ppb that poses health risks
as a solution is not viable public policy.
Another concern of EPA managers is that use of a lower dioxin cleanup level could affect
regulatory permitting and public acceptance of various industrial and waste management facilities.
TI1is raises a conflict between protection of public health and concerns about impacts on sources
of dioxin, such as industrial and municipal waste incinerators. As Silbergard and deFur observed,
"much of the continuing delay by government 111 implementing comprehensive management of
[dioxin] risk arises not only from scientific uncertainty but also from the politics and economics of
controlling specific dioxin sources."
An attractive delay strategy for Superfund managers is waiting for EPA's final dioxin
reassessment, because it is commonly understood it will take years to complete. TI1eir risk
management means letting successors inherit this problem. The final report is not likely to
remove the fundamental problems with the 1 ppb level. The dioxin soil cleanup issue has been
successfully kept at the Superfund program level, allowing EPA to ignore its inconsistencies with
larger agency goals and commitments. EPA's continuing use of 1 ppb, however, w1dermines its
goals of using good science, common sense, and risk management to improve decisions and
public confidence. Ultimately, there are institutional risks and penalties that can only be
minimized by taking the initiative to co_rrect the dioxin cleanup problem. Ironically, the 1 ppb
level was a consequence of an EPA crisis in 1983 and it could precipitate another one.
EPA's inability to retreat from the I ppb level reveals more than bureaucratic inertia,
however. Over the past decade a climate of bureaucratic loyalty has emerged. It intimidates
lower level Superfund site managers and prevents them from departing from the "company line"
by using lower dioxin levels for cleanup and relocation decisions. This is difficult because as
front-line managers they get the demands from angry people for more effective dioxin testing and
cleanups and for relocation of residents. Defending EPA's 1 ppb is increasingly difficult.
12
Public perceptions
Policy aside, use of 1 ppb, rather than 2 or 4 ppt based on EPA risk methods, can only be
logically interpreted as either EPA rejecting its own risk assessment methods and results, or EPA
acting as if a dioxin cancer risk greater than 10-4 is acceptable, which violates the law. When
cleanup levels for other contaminants are set on the basis of 10-6 risk, either by means of risk
assessment or use of EPA's soil screening levels, use of 1 ppb is even more untenable. How can
EPA defend using its risk numbers for all chemicals except the more toxic dioxins?
Use of 1 ppb erodes public confidence in risk assessment, as revealed by advice given to
community groups addressing dioxin cleanup sites: "It doesn't matter if the risk level is one-in-a-
million, one in-one-hundred thousand, or one-ten thousand. [N]o amount of additional exposure
is acceptable and a risk assessment approach that attempts to define a negligible or acceptable risk
is irrelevant. "24
The public, now well informed (some would say inflamed) about dioxin also knows that
non cancer health effects are now probably more significant than cancer, particularly if synergistic
interactions with pesticides and PCBs occur. For noncancer effects, ATSDR staff have shown
that dioxin levels much lower than 1 ppb are approptiate. All the available scientific information
support using low ppt dioxin TEQ for cleanup and relocation decisions .. The scientific community
has sent a clear message that there is no safe level of dioxin exposure. The ubiquitous presence of
dioxins should cause cleanup decisions to recognize other exposures, not to dismiss levels of
dioxin below 1 ppb because "dioxin is everywhere." EPA's use of I ppb literally adds insult to
lllJUI-Y.
Conclusion
This risk, historical, and policy analysis provides support for new EPA Superfund
guidance that specifies the 2 and 4 ppt levels for residential and cleanup site soils, but permits use
of different dioxin TEQ levels if they are supported by site specific information. The guidance
should clarify that chronic health effects other than cancer should be considered, that past and
other sources of dioxin and PCB exposures should be accounted for, that control samples should
be used to determine background levels, that EPA method 8290 should be routinely used, and
that non-detects should be converted to onehalf their actual method detection limits to calculate
TEQs. The guidance should also clarify what types of sites should be tested for dioxins in soils,
because cases have arisen where either no dioxin testing was performed or where the testing was
performed very late in the Superfund process, even though site information supported dioxin
testing. EPA could also provide a framework for evaluating past decisions and whether there are
grounds for reexamining them
13
References
1. RD. Kimbrough et al, Health Implications of2,3,7,8-Tetrachlorodibenzodioxin (TCDD)
Contamination of Residential Soil, J. Tox. and Env. Health, v.14, pp.47-93, 1984.
2. EPA, memo by J. Winston Porter, head of the Superfund program, to Barry Johnson, head of
ATSDR, Jan. 26, 1989.
3. EPA, Health Assessment Document for Polychlorinated Dibenzo-p-Dioxins, EPN600/8-
84/014F, 1985 .
4. EPA, National Dioxin Study, EPN530-SW-87-025, 1987.
5. EPA Region 3, Risk-Based Concentration Table, April 19, 1996; Internet at
http ://www.epa.gov/reg3hwmd/riskmenu.htm?=Risk+Guidance.
6. L. M. Gibbs, Dying From Dioxin, South End Press, Boston, 1995. pp.39,42,8.
7. U. Jarnberg et al, Polychlorinated byphenyls and polychlorinated napthalenes in Swedish
sediment and biota: Levels, patterns, and time trends, Env. Sci. Tech., v.27, pp.1364-1374, 1993 .
8. D. J. Paustenbach et al, Recent developments on the hazards posed by"2,3,7,8-
tetrachlorodibenzo-p-dioxin in soil: implications for setting risk-based cleanup levels at residential
and industrial sites, J. Tox. Env. Health, v.36, pp.103-149.
9. A O'M. Bowman, Epilogue, in The Politics of Hazardous Waste Management, J.P. Lester
and A O'M. Bowman, ed~., Duke Univ. Press., 1983, p.253.
I 0. H. Pohl et al, Public Health Assessment For Dioxins Exposure From Soil, Chemosphere,
v.31, pp.2437-2454, 1995.
11. T. Colborn et al, Our Stolen Future, Dutton, New York, 1996, pp.120, 181.
12. EPA, Soil Screening Guidance: Technical Background Document, EPN540/R-95/128, May
1996.
13. E. K Silbergard and P. L. deFur, Risk Assessment of Dioxinlike Compounds, in Dioxins and
Health, A Schecter, ed., pp.51-78, Plenum Press, 1994.
14. S. E. Hrudey and D. Krewski, Is There a Safe Level of Exposure to a Carcinogen?, Env. Sci.
Tech., v.29, pp .370A-375A, 1995.
15. S. F. Arnold et al, Synergistic Activation of Estrogen Receptor with Combinations of
Environmental Chemicals, Science, v.272, pp.1489-1492, June 7, 1996; S.S. Simons, Jr.,
Environmental Estrogens: Can Two "Alrights" Make a Wrong?, p.1451; J. Kaiser, New Yeast
Study Finds Strengths in Numbers, p.1418.
14
16. EPA, Estimating Exposure to Dioxin-Like Compounds, Vol. I: Executive Summary, Draft,
EPA/600/6-88/005Ca, 1994.
17. S. B. Floit et al, Evaluation of the Use of Substitution Methods to Represent Nondetect Data,
in Superfund Risk Assessment in Soil Contamination Studies: Second Volume, ASTM STP 1264,
K Hoddinott, ed., Amer. Soc. for Testing and Materials, 1996, pp.70-83.
18. EPA Region 5, memo from J. Milton Clark, Health Effects Specialist, to George A Jones,
Chief: Superfund Implementation Group, July 30, 1995.
19. G. R Nemeth et ai Background Determination of Element and Anthropogenic Compounds
in Soils of the Maryland Coastal Plain, in Superfund Risk Assessment in Soil Contamination
Studies: Second Volume, ASTM STP 1264, K Hoddinott, ed., Amer. Soc. for Testing and
Materials, 1996, pp.3-18.
20. EPA Region 4, South Tifton Residential Area Investigation Report, Tifton, Georgia, Sept.
1995.
21. EPA, memo by D. Clay, head Superfund program, to EPA Administrator, Feb. 27, 1992.
22. GAO, Superfund -Information on Current Health Risks, GAO/RCED-95-205, 1995;
Superfw1d -Improved Reviews and Guidance Could Reduce lnconsistenties in Risk Assessments,
GAO/RCED-94-220, 1994.
23 . EPA, Superfund Innovative Technology Evaluation Program-Technology Profiles Seventh
Edition, EPA/540/R-94/526, 1994.
24. S. Lester, Risk Assessment and Dioxin, Everyone's Backyard, v.14, n.2, pp.24-26, 1996.
15
~R OH 9197153605 SOLID WASTE DIU
'
~BMORANDUM
I
!
I
I i.o:
1
I I
Bill Meyer
Joel Hirschhorn
Patrick B~es
Mike Kellf
I
i . .
10.21.1996 13:38
21 Ootober 1996
.DRAFT Rf P FOR DIOX/NIFURAN ANALYSIS
i
i I have quickly worked on a Part h, Scope of Work, that would be luded in a RFP sent
J I
o~t to the laboratories to do the dioxin te~ting, I have alao included the list flabs with whom I
i I
. ~ve spoken. This list cwhe off of the Ji1t of EPA approved laboratories for ioxin testing.
I ;
1 .
, I wanted to get something to you ~oday in cue this was an issue you anted to discuss at J techni 1 ' l J° ca meetma.
i
F'. !
F~~M 9197153605 SOLID WASTE DIU 10.21.1996 13:39
October 18. 1996
ME~ORANDUM
To:j Bl~L MEYER I JOEL HIRSQHHORN
· PATRICK BARNES
FRJM, MIKE KELLY
SU~JECT: DIOXINIFUllAN ANAL Y~IS
! I l . : .
j I have made contact with several laboratories across the country In res ds to possibly
doi~g dioxfn/furan analysis for us on an esitmated 40~5 samples. As you kn , we have used
thejrriangle Lab'.s facility iq Durham in th~ past u a sole source (only one in orth Carolina. and
Eat Coast .. that 1 know of). • .
J I i .
· A couple of week& ago I visited ~ toured the Triangle faolllty and as ed thelr
m 1agement to give us a Wtter price on estimated 40 samples. They have ffered us $875 per
•~pJe. They also will supply the contain, rs and for an 9;'1ditional $1,200-1,S 0 (dependina on
on o~ two days), •upply a field person and a courier sorvJce to pick up the pies and take
cu tody of them 'from us at1he landfill. i
. . '
! In order to sole source. such a Jarsd sum, I had to first check with othe labs to see what
th~ir prlcini would be for this larger number of samples. What I have found s that variable
pr~cing is availa~le from the $700-900 ratjge. One lab even said $625 each, t would require us
to pay for 4 additional blanks which raise$ the unit cost somewhat. Two of e labs have people
in ihe triangle area and could send someo~e to the site to collect the samples om us, but we did
no\ get into the pricing of that. Others (TfxU, Oklahoma, Missouri) may no be in a good
p~sition to send. someone or even quote op this servJce. Normally, samples put into the chain
ot
1
custody and &hipped vla federal expresr,
. I
/ I would suggest that this issue be ~iscusscd with the technical group d that we send out
a ♦hort request for quotation to each of the 6 labs I have spoken with and iss e tho order to that
fa,bility offering us the best price and senlice. All of them are on the BPA ap roved list for
d~oxin testing. This would not be as co~licated as the well digslng and th efore could be
a complished ip 2-3 weeks (request for quote to lsaulng purchase order). I lll be working
t wards that type of resolution until I heb otherwise. I I
j !
I
P. 2
I '
I.
!ROH 91971~3605 SOLID WASTE DIV 10.21.1996 13:39
I
l Part II .
sJpe of Work:
1
2.~ Background on Watren County PQB Llllldfill
2.0.1
2.0.2
2.0.3
'
The State of North Carol~ (State) owns and maintains a clo d (July 1983)
polychlorinated biphcnyl (PCB) chemical waste landfill penn· ted in accordance
with the Toxic·substance qontrol Act (TSCA) and 40 CPR P 761.
' i
The PCB landfill is locat~ on the East aide of SR 1604 appro imately 1,S to
2 miles from the intorsccti~n of SR 1604 and US 401 South, 3 miles
from Warrenton, North Ciolina.
I
The State has established• loint Warren County/State PCB
Working Oroup (Working'.Oroup) to evaluate technologies
with the detoxification of the landfill. The Worldng Group h hired two Science
Advison to work with the'. Group and the State and any other ntlty through this
project.
2.0.4 The purpose of this RFP i~ to iolicit laboratories interested i providing dio,dn/
furan testl~g on a vuiety ~f samples to be taken from and ar d tho landfill,
Md, at the discretion of the Workina Oroup, bo prepared top vlde an Individual
to be on ha,nd for the sampling event and to take custody of e samples at the
landfill. /
Concept 6f the operation
2.1.1 Members of the Division '.of Waste Managemont, with the So ence Advisor's,
will be responsible for t~ing all 1amplcs at the site. It is c ently estimated
2.12
2.1.3
that the samplins event ~II require two days, ~d hopefully e place within the
next 4S-6Q days. ·
' I One of the Science Advi~ora will assign the code• to all sam les and maintain the
master ro•ter. A draft s$plins plan hu been completed an will be made
available to the contractor for the dioxio/furan analysis.
i
Bach prospective bldderi· hould include a separate cost esti !lte for
providina one or two sta . members on site to take custody f the samples and
ship to th~ laboratory. I this is not possible u a result of la location or
ave.ilabili~y ofpersoMel) please note on the bid. Abllity to omply with 2.1 .3 is
not an abiolute in order 'o be awarded the contract.
P. 3
. F~OM 9 1~7 1~3605 SOLI D WA STE DI U 10.21.1996 13:4 0
I
I
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l
2)3
I
[ff] ill bJ ~ u llJW
I
2.1.4 It is estimated that there will be a minimum of 40 and a m mum of SO 11amples
within the following ca~goriea ~d current estimates:
W~JI water
L~chate
Surfa¢e water
Sediment
sous '
Filter bed
Blanks
Estimate 18
Estimato02
Estimate 06
Estimate 04
Estimate 06
Estimate 02 . ' Estimate 06
Tho laboratory wltl be re•ponsible for providing appropriate ntaincrs for all
samples and to pay shipplna costs. ·
I
'
2.1.S All analytical work 'Will follow the Method 8290, full Tetra• eta scans and a Level
III RePort summary pac*ge for the samples and calibration aw data. An
example of the reporting format should be includod ln the bi packaae. All
results are to also be repo,rted In a table fonnat showing sam le numbers and
results as • single dlmdn ~umber.
I
I .
2.1.6 Each bid package should ~ndicato what the standard tum aro d time ls for sample
results, as well as include' a specific matrix for costs usoclat with quick turn
around in ? and 14 days. i ·
Deliverables
2.2.1 BJd options should inclu4o the following:
• Unit prlc~ per sample !
-Tum around time, cost ~ expedite
, I
• Sample ~port :
• Cost to mobilize 1-2 in~ivJduals to receive samples at the 1
-Overnight shipping charges for samples
• Cost for &ample containf rs, if charged separately
-Other-any other items 'thich may need to be considered in e cost estimate
• List of S tef erences l ·
.. Required prior notificati;on for start•up of work.
I '
Criteria for selection ofresponde~t
i
2.3.1 Demonstrated experiencc :and qualifications in dioxin/furan t sting
2.3 .2 Cost of bid optiom i .
2.3.3 Past perfonnancc with rc~pcct to working rclationshlpa with lienls
2.3 .4 Cepabilities
"· 4
,FROM 9197153605 SOLID WASTE OIU
!
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I
10.21.1996 13:41
LaJ,o~toda to lie 1pHQlted;,
Trianale Laboratories
Durham,NC .
2.1 Twin City Testing :Corp. l St. Paul, MN
!
i i i ! l
l
Southwest Research Institute (SWRI)
San Antonio, TX · I I
Midwe,t llesearch lmtituto (M~
Kansas City, MO i
I
Ionics Internatlon'1, Inc I
Houston, Texas ·
Southwest Laboratory of Oklaho~a
Broken Arrow, OK 1 I
P . 5
Sept. 3, 1996
To: Bill Meyer .................................................................................... by FA.,"'X
From: JoelIIirschhom
Subject: responses to vaiious faxed questions received on 8/29/96
1. As I have told you, I believe that Triangle Labs does good testing for dioxins. You have not
indicated whether they have given you a quantity price. You suggest the option ofissning an
RFP, but I do not know whether doing so will delay any analyses of clio,dll, .nor whether the labs
on the list you sent are in EPA's CLP program. Even when method 8290 is used, I notice that
some labs have unusually high detection limits. I also expect all data to be reported by the lab to
include TEQvalues for each sample, foUo,ving EPA's procedure ofusing onehalfthe actual
detection limit for nondetects of individual isomers.
2. A.s to the lists of reporting values you sent, are they from your state lab? I do n.ot understand
the use of.reporting values. Are you saying that non-detects are reported as these? I exi,ect to
see method detection limits for the actual tests conducted (i.e., not generic ones). All the lists
received were for liquids, none for solids. I would like to know whether\the lab can test for PCB s
and obtain a detection limit less than 100 ppb. Tl•e list for organic e:x1ractables is incomplete; I
ex'Pect to see tests conducted for all major P AHs, especially benzo( a )pyrene; here too I would like
to kno\v whether they can achieve a detection limit less than 100 ppb.
~21C
~og//
~/ ttf/
~210 i
/3 II
I I
I
y
STATE LABORATORY OF PUBLIC BEALTB
PO BOX 28047 -S06 N. WlLMINGTON ST •• RALEIGH. NC 27611
ORGANIC CHEMICAL ANALYSIS
P[,'RG.F.ABLE COMPOu'?IDS LJ!.l3NO
FIELD NO
COMPOCJN.O TYPE ( ) ( ) ( ) ( ) ( )
~,~ft ppb ppm ppb fPrtl (Jpb pp,f"! ppb ppm -fFb ppm:
l>ImlOMOKll:T~ 5
~~P!!NTANO!fl: ,o
a&-1.3-DtCBLOROnon~ 5
TOJ.mn ..
TRANS-l.3.-l)1cm.o~onon:m:
1.1,1,2. 'l"rrllAC:U:X.OR~
1.l~nm:m.C>R.Onl?A.~ '\/
Z.li:C'A~O.'ff; JO I
T:l'RACRLORO~ 5
P1l1~0MOC.'U.Ok¢Klll:'niA.'m I
r:rznL~ J::)l::BJtOXIDE
CBl',()JrOl!IE~
1,l.1,:2-n:=Ac:31.0ROI!:".:'~
1':"!"a'lL lllc,:z:El'fl!:
~NES
Sl"TRZ.'il': '\ I
UO.Y.OP'Q.UC iO
TltAlffl,1."-DlCBLOR0-2-B'C'r2NE io
1,1.3,.-Tmcn.()R.0:l'RCP~ ..5
1 • .&-DICl!l.OROS~ l
1,1.mcm.oaon~ '1,1
1-'•CDmOM:0•3-CHLOROPRCPANlt c?,t>
VZ?fTl,J,.ct'tATZ ;iLJO
C ~ i'r-~:s,al.(: Ll~io (<:.:-.,1=n-A1)..lt:nc::N OP-. 8RCC:.G-KCu.-.jr_;,
J -Xsti:mated Talue
r:: -A<:t.uiu. Tal.ua .i:t ltnowr. to be less than ..,_lu" given.
L -Actual Talu• i ■ kno'>m to be gre~t~r than v~lu~ giv~n.
.,
I
V -Xaterial. was e.naly:ad fo~ but ~ot dot•ctad. Th• n=ber i• the Minil::n.= ~t•etion Lil:dt.
l'Q. -Not -ly:ad.
1/ -Tentative identi~ic~tio~.
3_/ -coMFol.l.t•H: Rf>...!f'-BLY PctECTABlE. ,:'.,\EY j/',! HIG·H {(1 .!ctNl'"RAi iC~):_j_ ✓··:S.:1NP;_r:: Hl~-HLY t,;s_;,.::-l'-Eu. t,-;DL'"'.'J De ,v_;,,· t~r'f',..:•I.
DEE?ra. 3088-0 {lO/93)
( )
ppb ppm
;
:I
..
1
I
· PURGc::OM.ORG
I I I
I I
I
l
STATE LABORATORY OF POBLIC HF..ALT.E
PO BOX 28047 -306 N. WILMINGTON sr .. RALEIGH. NC 27611
ORGANIC CI.lEMl'CAl, ANALYSIS
LAB NO
FlEU> NO ... _
COMPOUND TYPE ( ) ( ) ( ) { ) ( )
MOf,}5 fppb PPb ppm ~b ppm PPb ppm ppb ppm ppb ppm,
CHLOROME'l'BANl: .JO
VINTI. cm..o:Rmlt ,o
llR.OlllcnttrHAl'fl!: d,0
CHr..ORO~ iO
TlrlCSI.Ollonm>ROJllL':tHAln! JO
,\Cl!:l'Omt ;;J..Q -l.1..J)lc,:LOR.01:l'B!:NI!: ~
10.COIIGTBA!fl!: I
~ cm.oxm,: l
CARJIOl( X)fS.JUII)~
':'l?Affll-1.2-:t>xcm.oaornm."fX ,,r
Aea'n.O~ ;u:i
1. l • DlCJ!ll.OROJt":BAK!: 5
2-'AUT.-\o'fO!m ;.>_D
~1.:U>Icm.c)RO~'lt 5
r,a.;.()RU1'0llUA i I
1,1. l•TlUClILORO!:nt.11'.'a: I
CM<l3(»I n:TJtACm.Cl:RlDE I
~ I
l.2-'Dicm.oROETB'.Affll: I
1'R%ClI..ORO~ j
1.2.:,tcm.o!lO~Cl'A?a: I l
BROMCD1C3U)~OIIUBA."a: ~
-C• f"c,~~.a .... :..AP., ~~>-!,tl'tf'''H!'H~, ,ON cR Bi~o::.CrRc ... a•.JD.
J -?a~i:ia~9d v&lu•
X -Act~al T~lue i• Jc=wn to b9 les~ thllll Tslue given.
L -Actual Talue 1• 'la:lown to b.. gx•at•~ than Talue givan.
U -Material wa8 ~lr-ed fo= but not detected. 'l'he number i• the Minimum. ~cectio~ ~ild.t.
1'DI. -Hot a=alr-ed.
1/ -T•ntative identi!ie~tion. 1./ ~ ~}'i\f'o ... ~o Ral ~91..'f OE..TEGRBU:.. ON~ IN fHcH C~NT"R,;ftcNS.
V -.SAAf't.'-HllmL'f OILl.\n?..o. f.i\OL!-:i> 00 ~ Ftf PLY.
DEcll'ra ~065--0 (10/93)
( )
ppb fPft"J
I
}'URQCOM.ORG
' .,.
B.'.SUNEUTAAL AAO ACIO
EXTRACTABlES
ca-lPOONO
m~ne
?nzicHne
,tv1 benzvl ohtha late
?nifa)~nthracene
1rysene
3--d1chlc:"l)benz~d1oe
is(2~thv1hexvl)~hthalate
i-n-octvl ohthalate
!nZO(b)fluoranthene
?nzo(k)fluoranthene
~.a)pvrene
,deno(l.2.3-<:d}ovre-oe
ibenzo(a.h)anthracene
?l'IZO(ci. h. i)oe1~1lene
n11ioe
~zoic acid
enzy_l ~ i cohO l
-cnloroan1 line
ibt?nzofuran
-methvtn.lc;hthalene
-met.',v 1 ohero l
-'tl?thvl Pheoo 1
...ri i tro.1n 1 l i ne
-..i i t,"Oan i 11 ne
-nitroanil ine
,4,S-tr1chlCMX>henol
STAiE LABORATORY OF PUBLlC HEAL TH
P.O. BOX 28047 -306 N. WlLMlNGTON, ST., RALEIGH, N.C. ?76ll
OOGAAIC 0181lCAL ANALYSIS
LAB HO
FIELD#
TYPE ( ) ( ) ( ) ( )
UNITS
·1r,/~=1~
1~4:JhL~r,
/()/~~
I 'Y'.
_t:;h///,.9')
Jr,I~::V,
10./:/.:/n
l.iC",; /J,_ c:-,., ,,
J ,.,
s:;-n/11.~
:
:
' I
1n1 =?=?a I ,
.. ,
..iv,, '1/.,,,.t::°LJ
I .
'
"ffl-D'-
I -Estimated VdlCie. H-::.0/.SOIL
, -Actual value is lcnown to be less than v.alue given .
( )
. -Actual value is known to be greater than value given.
J -N.iterial wa,; analyzed for-but not detecte<:1. The n~r
IA -Not .an.al:i,ze<i.
1s the f11ninun {)ete<:tion Umit. (n,\~l-) ---
l/ -Tent-ltive identification. 11 -On NROC li~t of Priority Pollutants.
( )
I
I
'-'"-J~ .:;.:..;;..-_/ .L -1-,'U ,::..•....1 -.,___, I l '~WI I L I 11 11 , -., , -, ,,_._.., .._, ,_-.._,
BASE/NEUTRAL ANO ACIO
EXTRACT ABLES
~POUND
N-n i trosodimethv l ,nine
bis(2-ch1oroethvl)ether
2-chlorc.ohenol
Oher.oi
1 3-dicnlorooenzene
1 4--dichloroben7.ene
i. 2-di ch lorobenzene
bi-s {2-ch loroi sooroovl )ether
hexachloroethane
N-nitroso-di--n;,rcpylam1ne
nitrooenzene
i~hOrone
2--0itroohenol
2.4-d1~thvloh-2nol
~is(2-c:hloroet~oxy}methane
2 4-dichlorooheool
1,2,4-trichlorobenzene
naohthalene
hexachlorcbutadiene
~-ct\ 1 oro-m-creso 1
~xachlorocvclooentadiene
2.4.f-trichloroohenol
2-ch1oronaohthalene
a~nhth,,lene
dimethvl phthalate
2.6-dinitrotoluene
acen.aohthene
2.4-dinitr00heno1
2 .. 4-dinitrotolueoe
4~itl"OOhenol
fluarene
4-d'iloroohenvlohenvlether
diethyl chthalate
i,6-dinitrc-o--cresol
d10henvlamine
.1zcbf.!1'12:ene
4-brarw:ohenvlchenvlether
hexachJorcbenzene
Of"nta.ch 1 orooheno l
ohQnanthrene
anthraceM
dib1-1tvl ohthalate
fl uoranthene
J -Estimated valoe.
STATE t.A80RATORY OF PUBLIC HEAlTH
P.O. BOX 28047 -306 N. WILMINGTON, ST., RALEIGH, N.C. 27611
ORGANIC 01EP1ICAL ANALYSIS
LAB HO
FIELD fl
TYP€ { } ( ) ( ) ( )
UNITS
l~./!r.1~
I
..
I
~-Rl,Q]
1,10/:t~,t
~/Jta!!!b
10/.~:;D
' .5CI f£,~~
JL!J/~2"1
~
' .L',;~/11~
IJtJ/~~I'}
. ,,
K -Actual value 1s k~n to be less than value given.
( )
L -Actual value is known to be gM?ater than value given.
u -Matffial was analyzed for but not detected. The nl.ll'ber
NA -Not analyzed.
is the 11i n inun Oetect 1on limit. (1'12)L..) ---11 -Tentative 1dentif1cation. y -On NRDC Us! of Priority Po1 lutants.
( )
'
NC Department of Environment,
Health, & Nawral Resources
Solid Wute Management Divi,ion
SA."¼PLE ANALYSIS REQUEST State Laboratory of Public H~lth
P.O. Box 28047, 306 N. Wilmington St.
Raleigh, North Carolina 27611-8047
Site Number _______________ Sample ID Number/Name _________________ _
Name of Site _______________ Collected By ______________ ID# ______ _
SiteLoC3tion Date Collected Time ---------------------r-:_-:_-:_-:_-:_-:_-_-_-:_-:_-_-:_-:_-:: __ ==========::::::::::::--,
Agency: Haz.u-dous Waste Solid Waste _._ Superfund TCLP Compounds
Sample Type Inorganic Compounds Results(mg/1)
Environmental Concentrate Comments arsenic -barium -
-Ground Water (1) -Solid (5) cadmium -chromium -
-Surface Water (2) -Liquid (6) lead -
-mercury
-Soil (3) -Sludge (7) -selenium
silver -
-Other (4) -Other (8)
Organic Chemistry Inorganic Chemistry
Parameter
P&T:GC/MS
Results (mg/I) Parameter Results(mg/l)(mg/kg) Organic'~onipo~ds Results(mg/1)
Acid:B/N Ext. -2,4~D -
-2,4,5-TP(Silvex)
chlordane -
-heptachlor
hexachlorobenzene -hexachlorobutadiene -endrin -lindane -
-methoxychlor
-toxaphene
----
FOR LAB USE ONLY
Date Received
Date Extracted
Date Analyzed
Reported By
Date Reported
Lab Number
----------
----------
----------
----------
DHS 3191 (Revised 12/93)
--
-
-
-
-
-
-
-
--
-
-
-
-
-
-
---
-
-·---
---
-
---
-
antimony
arseruc
barium
beryllium
cadmium
chloride
chromium
cobalt
copper
fluoride
iron
lead
manganese
mercury
nickel
nitrate
selenium
silver
sulfates
thallium
vanadium
zinc
pH
conductivity
TDS
flash point
_ benzene
-carbon tetrachloride
chlordane
chloroben.zene
chloroform
o-cresol
m-cresol
p-cresol
cresol
1,4-dichlorobenzene ______ _
1,2-dichloroethane
1, 1-dichloroethylene ______ _
2,4-dichloroethylene ______ _
heptachlor
hexachlorobenzene
hexachlorobutadiene ______ _
... hexachloroethane -_ methyl ethyl ketone
nitroben.zene
_ pent.achlorophenol
_ pyridine
_ tetrachloroethylene
_ trichloroethylene
_ 2,4,5-trichlorophenol _____ _
_ 2,4,6-trichlorophenol ______ _
_ vinyl chloride
endrin
lindane
methoxychlor
toxaphene
2,4-D
2,4,5-TP (Silvex)
DRAFT SAMPLING AND ANALYSIS PCB LANDFILL
SAMPLE ID
LOCATION
LEACHEATE
PCB
19LEACHEATE INLET
20 LEACH EA TE OUTLET
SAMPLE ID
LOCATION
SURFACE WATER
21 SW-1 SOUTH UT NEW
22 SW-2 SOUTH WEST UT NEW
23 UTUS EXISTING
24 RCUS EXISTING (Below Bridge)
25 RCDS EXISTING
26 RCUS NEW (Above Bridge)
SAMPLE ID
LOCATION
SEDIMENT
27 USSS-ABOVE BRIDGE ON RD
28 BB BELOW BRIDGE ON RC
29 SS-1 SE DRAW ON UT
30 SSND N DRAW ON RC
SAMPLE ID
LOCATION
POND SOIL
31 PS-1 OVERFLOW PIPE BASE
32 PS-2 CENTER OF POND
33 PS-3 DISCHARGE PIPE OUTLET
SAMPLE ID
LOCATION
BLANKS
34 TRIP 1
35 TRIP 2
36 SOIL 1
37 WATER 1
38 WATER-2
39 WATER-3
40 HYDRO PA
41 LANDFILL SOILS
PCB
✓
✓
✓
✓
✓
✓
✓
✓
DIOXIN/ BN/AE
✓
✓
FURAN
PCB
✓
✓
✓
✓
✓
✓
PCB
✓
✓
✓
✓
PCB
✓
✓
✓
✓
✓
✓
✓
DIOXIN/
FURAN
✓
✓
✓
✓
✓
✓
DIOXIN/
FURAN
✓
✓
✓
✓
DIOXIN/
FURAN
✓
✓
✓
voe
DIOXIN/
FURAN
BN/AE
✓ ✓
✓ ✓
✓
✓
✓
✓
✓
✓ ✓
METALS
✓
✓
voe
✓
✓
✓
OTHER
✓ ✓
✓ ✓
METALS OTHER
✓
✓
✓ ✓ .. Other for landfill soils include particle size distribution engineering classification, liquid limit, plasticity index, moisture
content, organic matter, nutrients
DRAFT SAMPLING LOCATION/ANALYSIS PCB LANDFILL
ANALYSIS
SAMPLE ID
LOCATION
GROUND WATER
1 MW-lA-NEWEAST
2 MW-lB-NEWEAST
3 MW 2-EXISTING NW
4 MW 3-EXISTING WEST
5 MW-3A NEW WEST
6 N2-4 EXISTING SW
7 MW-4a NEW SW
8MW-5NEWN
9MW-5aNEWN
10MW-6NEW S.EDRAW
11 MW-7 NEW SOUTH
12 MW-7A NEW SOUTH
13 MW-8 NEW N. E. DRAW
14 MW-9NEWN. DRAW
15 MW-l0NEWW. DRAW
16 BACKGROUND WELL 1
17 BACKGROUND WELL 2
18 BACKGROUND WELL 3
PCB
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
DIOXIN/
FURAN
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
✓
BN/AE voe METALS OTHER
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
✓ ✓ ✓ ✓
Background wells located 1-2 miles off-site in NW, SW and SE quadrants. Attached is list of constituents and
detection levels for each analytical test. Wells m2-6,8,9 and 10 may require a nest ifhydrogeological
conditioning warrants.
Total Samples/ Analysis
40 total; PCB 40; Dioxin/Furans 40; BN/AE 23 ; VOC 23 ; METALS 23 x7= 161 (As, Ba, Cd, Cr, Pb, Hg, Se)
07/24/96 08:33 FAX
July 24, 1996
Mr. Jack Butler
Superfund Section
PO Box 27687
Raleigh, NC 27611
Dear Mr. Butler:
BILLIE ELMORE
This letter is in response to your request that I put my questions
in writing concerning the disposition of the contaminated soil at
the Kopper Chemical Site at Mooresville and the fate of the BCD
Trials that were conducted there.
In my telephone conversation with you, I specitically wanted to
know what went wrong with the BCD trials that were conducted at
Mooresville? What were the emission levels of what toxics that led
to discontinuation of the BCD trials? Bow much did these levels
exceed the North Carolina standards? What alternative technology
or technologies were or are being used to remediate the Ropper's
site?
After learning that BCD trials with unacceptable dioxin emissions
in California played a part in the decision to abort this
technology, I wanted to know where in California and what company
conducted those trials and what were the unacceptable dioxin
emissions levels produced there?
After you told me that the contaminated soil was shipped to
Kentucky for incineration, I further asked the name of the
incinerator company in Kentucky and the levels of dioxin in the
contaminated soil shipped to this company for incineration?
My last requeat to you was that you fax me information to these
questions in writing to Pax: 919-774-7498, which you agreed to do.
Thank you so much for answering my questions on the phone and I
look forward to receiving your written answers as well.
Sincerely, ,
~~~--·
Billie Elmore
5301 Rolling Rill Road
Sanford, NC 27330
Tel[phone]
!d,1001
State of North Carolina
Department of Environment,
Health and Natural Resources
Division of Solid Waste Management
James B. Hunt, Jr., Governor
Jonathan B. Howes, Secretary
William L. Meyer, Director
Ms. Billie Elmore
5301 Rolling Hill Road
Sanford, NC 27330
RE: BCD Technology
Dear Ms. Elmore:
AW ... ~_~_.
DEHNR
July 30, 1996
Thank you for your letter of July 24, 1996 requesting information on the BCD pilot
demonstration at the Koppers Superfund Site at Morrisville in Wake County. Below are the
answers to the questions that you asked:
• ... what went wrong with the BCD trials ... ? What were the emission levels of
toxics that led to discontinuation of the BCD trials? How much did these levels
exceed the North Carolina standards?
Answer: During the design phase, the North Carolina Superfund Section and the
citizens of the Shiloh Community were assured that there would be no releases of
dioxin to the atmosphere during the test. Contrary to the assurances, outlet sampling
and mass-balance calculations by the USEP A suggests that as much as 0.3 grams of
dioxin were rdeased to the atmosphere during the test. One high-volume air monitor
device used c:•: -ing the demonstration detected 4 pg/dscm diexins. The state ambient
air guideline for dioxin is 3 pg/dscm on an annual basis.
• What alternative technology or technologies were or are being used to remediate the
Kopper's site?
Answer: The ponds at Koppers were drained, the water treated with carbon filters and
released. The released water was handled according to the substantive requirements
of a discharge permit. The soils contaminated above the remediation level were
excavated and shipped to the L WD incinerator in Calvert
P.O. Box 27687,
Raleigh, North Carolina 27611-7687
Voice 919-733-4996 lfffi&lliJMN
FAX [phone]
An Equal Opportunity Affirmative Action Employer
50% recycled/10% post-consumer paper
Ms. Billie Elmore
July 31, 1996
Page 2
City, Kentucky. The drained ponds and the excavations were backfilled with clean
soil. The contaminated groundwater will be remediated by pumping a recovery well.
The pumped water will be cleaned with carbon filters and released to a drainage
ditch. All of this work has been and will be conducted according to a performance
verification plan. ·
• ... I wanted to know where in California and what company conducted those trials
and what were the unacceptable dioxin emissions levels produced there?
Answer: A pilot-scale BCD demonstration was conducted at the McCormick &
Baxter Superfund Site in Stockton, California. ETG Environmental, Inc., the same
company that performed the BCD demonstration at Morrisville, conducted the pilot
test in California. Following the California demonstration, USEPA estimates the
following dioxin levels resulted from atmospheric releases during the test: 17
pg/dscm at the fence line, 31 pg/dscm onsite and downwind, and 217,000 pg/dscm in
the exclusion zone. These levels greatly exceeded the performance goals set prior to
the demonstration.
• ... the name · f the company in Kentucky and the levels of d: ;-1xin in the
contaminater., ,.)il shipped to this company for incineration?
Answer: The soils were shipped to L WD Inc. in Calvert City, Kentucky. This
facility is regulated by the Kentucky Department for Environmental Protection. In
March of this year, the LWD incinerator was visited by an engineer from the
Superfund Section, a resident inspector from North Carolina's incinerator inspection
program, and representatives of the Shiloh Community group. The facility was found
to be state-of-the-art and operating according to Kentucky environmental regulations.
Based on the information developed during the Remedial Investigation, the maximum
dioxin level in the contaminated soil was 200 mg/kg.
I hope this letter provides the data that you require. You may find more information on
the Koppers Site in our files at the Superfund Section in Raleigh. These files are open to the
Ms. Billie Elmore
July31,1996
Page 3
public and you can make an appointment with Scott Ross at [phone], extension 328 if
you would like to examine them. If I can be of any further assistance, please call me at the same
phone number, extension 293.
cc: David J. Lown
Sincerely,
Jack Butler, PE, Chief
Superfund Section
Septcmber 18, J l)l)5
Memorandum
TO:
FROM:
RE:
Bill Meyer _ C ,',) {-j
David J. Lown /G(G
Dioxin/Furan Analyses During Performance Testing of the
SoilTech ATP System
Smith's farm Supcrfund Site
Bullitt County, K.cntucky
As you rcquestcd, I havc reviewed the Proof-of-Process Report looking for information
on dioxin/furan testing at the Srnith's Farm Superfund Site. Only one test for dioxin/furan was
done during the pcrlormance test. The lone test was a stack emission analysis completed early in
the study. The levd of dioxin detected during the test was 0.33 ng/<lscm total dioxin/furan
(Table 5). This concentration has a 2,3,7,8-TCDD toxic equivalent of .0097 ng/dscm
(Table 2-3). The state of North Carolina annual guideline for 2,3,7,8-TCDD is 0.003 ng/dscm
(NCAC 15A 2D .1100).
Attachments
cc: Jack 13utler
Compound
Total PCBs
lead
PAHs
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Chrysene
Dibenzo( a, h) anthr acene
ldeno( 1,2,3-cdlpyrene
Total PAHs except Naphthalene
Naphthalene
Particulates
Opacity
Total Dioxins and Furans
Total Hydrocarbons
Hydrogen Chloride
PAIH:1502-93\POPTS.XLS 16/23/941
TABLE 5
ST ACK EMISSION RATES
SMITH'S FARM OPERABLE UNIT ONE
BULLITT COUNTY, KENTUCKY
Units Window #1
lb/hr 7.69E-07
lb/hr ND (3.5E-05)
lb/hr < 3.4E-07
lb/hr < 1.3E-06
lb/hr <4.9E-07
lb/hr < 3.3E-07
lb/hr < 1.0E-06
lb/hr <4.9E-07
lb/hr 9.90E-05
lb/hr 9.30E-05
gr/dcsf 0.0009
percent 0
ng/dscm 0.33
ppm 6.0
lb/hr 6.1 0E-02
Window #2 Window #3
5.36E-07 9.00E-07
<4 .0E-05 ND (3.3E-05)
< 2.9E-07 <3.0E-07
< 7 .5E-07 < 7.8E-07
<4.3E-07 <4.3E-07
< 2.9E-07 < 2.9E-07
<8.6E-07 < 8.6E-07
<4.3E-07 <4.3E-07
8.B0E-05 8.B0E-05
8.20E-05 7.90E-05
0 .0002 0.0013
0 0
-----
7.8 8 .0
3. 78E-02 4.68E-02
SOILTECH ATP SYSTEMS, INC.
SHEPHERDSVILLE, KENTUCKY
RESULTS
Table 2-3
Exhaust Stack -Oxygen/Carbon Dioxide, Dioxins and Furana
Run No.
Date (1994)
Start Time (approx.)
Stop Time (approx.)
Gas Conditions
T1 Temperature (°F)
Bwo Moisture (volume%)
Volumetric Flow Rate
0 1 Actual conditions (acfm)
a,td Standard conditions (dscfm)
Continuous Emissions Monitoring
0 2 Oxygen (dry volume%)
CO2 Carbon dioxide (dry volume%)
Dioxin• and Furana
Total PCPPs and PCDFs
C Concentration (ng/dscm)
C Corrected to 7% 0 2 (ng/dscm)
C Corrected to 12% CO2 (ng/dscm)
E Emission rate (g/sec)
EPNBZ • 2,3,7,8-TCDP Egujyalent PCDPs and PCDFs
C Concentration (ng/dscm)
C Corrected to 7% 0 2 (ng/dscm)
C Corrected to 12% CO2 (ng/dscm)
E Emission rate (g/sec)
tTEF/89 -2,3,7.8-TCPD Egujyalent PCDOs and PCDFs
C Concentration (ng/dscm)
C Corrected to 7% 0 2 (ng/dscm)
C Corrected to 12% CO2 (ng/dscm)
E Emission rate (g/sec)
Revision O
1
May 10
09:55
12:58
173
23.54
5,566
3,486
8.4
8.5
0.29
0.33
0.41
4.8E-10
0.0087
0.0097
0.012
1.4E-11
0.013
0.014
0.018
2.1E-11
A-7
2-3
--rm ----== ---w ---WWW
EPA AND INTERNATIONAL TEFs
FOR DIOXINS & FURANS
TEF = TOXIC EQUIVALENCY FACTOR
DIOXINS
1.000 X CONC 2,3, 7 ,8-TCDD
0.500 X CONC 1,2,3, 7 ,8-PeCDD
0.100 X CONC 1,2,3,6, 7 ,8-HxCDD
0.100 X CONC 1,2,3, 7 ,8,9-HxCDD
0.100 X CONC 1,2,3,4, 7 ,8-HxCDD
0.010 X CONC 1,2,3,4,6, 7 ,8-HpCDD
0.001 X CONC OCDD
FURANS
0.100 X CONC 2,3,7,8-TCDF
0.050 X CONC 1,2,3, 7 ,8-PeCDF
0.500 X CONC 2,3,4, 7 ,8-PeCDF
0.100 X CONC 1,2,3,6, 7 ,8-HxCDF
0.100 X CONC 1,2,3, 7 ,8,9-HxCDF
0.100 X CONC 1,2,3,4, 7 ,8-HxCDF
0.100 X CONC 2,3,4,6, 7 ,8-HxCDF
0.010 X CONC 1,2,3,4,6, 7 ,8-HpCDF
. 0.010 X CONC 1,2,3,4, 7 ,8,9-HpCDF
0.001 X CONC OCDF
FROM t~C DEHNR-D I lJ LAB SERlJ ICES TO 53605
·· ·-----· ·----c-·-----·c ~-:._~U-~-----
·:'.: -~--~>:·: ·.:/' ·:,> ·;~.~·
~::.· ;-·;.,<~. --r-~-' ~:~v:~~~-1: :,
·-'~ 1:: -:,; .. :.' ... ~--~ +wo
V\ 0--0 e,, a: \ c v25~ s'-'-68" s.'t\' ~ s re~8J-..~ ~
Sr~¼~~Q--~ ~ »:o~~N,
. . .
(--z.-) fr\ ,i:ke_ s ~ ~ ~ ~
o.. &LI ~0-r "---1o l~ (}cAA._cJ?_ c ~::~ \-o
~ ~ ~s+-0,;v--~ ~;L~ : Vodoo l . ,_ , . ·-
11...v.,_.__ fV-rJ~-?:s I~~~-1s-,:,o ~~ .• ,.~;.•~o
I .,,-,,_> 0-,--~ µ ~ (N'.A-& . c.-~ s
..
" " ' ~~~~pt~~ V · ·.
9b ¼_,__ ~b d< l/V'-~.-.;'.i~c-,
WARWELLS.XLS WARREN COUNTY PCB LANDFILL PCB ANALYSIS IN MONITORING WELLS PARTS PER BILLION (PPB) MONITORING WELLS MW-1 MW-2 MW-3 MW-4 DATE 6/6/84 <0.1 <0.1 <0.1 <0.1 12/11 /84 <0.1 <0.1 <0.1 <0.1 5/24/85 <0.1 <0.1 <0.1 <0.1 11 /1 3/85 <0.1 <0.1 <0.1 <0.1 5/6/86 <0.1 <0.1 <0.1 <0.1 11 /18/86 <0.1 <0.1 <0.1 <0.1 6/4/87 <0.1 <0.1 <0.1 <0.1 2/2/88 <0.1 <0.1 <0.1 <0.1 7/6/88 <0.1 <0.1 <0.1 <0.1 3/21 /89 <0.1 <0.1 <0.1 <0.1 10/25/89 <0.1 <0.1 <0.1 <0.1 4/19/90 <0.1 <0.1 <0.1 <0.1 4/24/91 <0.1 <0.1 <0.1 <0.1 10/28/91 <0.1 <0.1 <0.1 <0.1 5/J 3/92 <0.1 <0.1 <0.1 <0.1 11 /24/92 <0.1 <0.1 <0.1 <0.1 Page 1
C. \ v ',
..
COMPARATIVE LEVELS OF DIOXINS AND FURANS
IN INDUSTRIAL WASTE CHEMICALS
WASTE OIL 1
WASTE OIL 2
RECYCLE OIL 1
RECYCLE OIL 2
MOTOR OIL
TECHNICAL GRADE
PENTACHLOROPHENOL
SOLITE WASTE FUEL
14.8 PPB OCDD
57 .6 PPB OCDD
27 .6 PPB OCDD
12.8 PPB OCDD
NON DETECTABLE
2,500 PPM OCDD
(2,500,000 PPB)
A 3.5 PPB OCDD
B 13.0 PPB OCDD
C 3.6 PPB OCDD
D 0.67 PPB OCDD
E 1 .4 PPB OCDD
OCDD -OCTACHLORINATED DIBENZO-P-DIOXIN
A,B,C,D,E Samples from actual fuel tanks at Solite
WARREN COUNTY PCB LANDFILL PCB ANALYSIS IN SURFACE WATER AND SEDIMENT SAMPLES PARTS PER BILLION (PPB) SURFACE WATER SAMPLES STREAM SEDIMENT SAMPLES RC-US RS-DS UT-US UT-DS RC-US RC-DS UT-US UT-DS DATE 6/6/84 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 12/11 /84 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 5/24/85 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 11 /13/85 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 5/6/86 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 11 /18/86 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 6/4/87 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 2/2/88 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 7/6/88 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 3/21 /89 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 10/25/89 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 4/19/90 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 4/24/91 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 10/28/91 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 5/13/92 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 11 /24/92 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 RS-US = RICHNECK CREEK UPSTEAM RC-DS = RICHNECK CREEK DOWNSTREAM UT-US = UNNAMED TRIBUTARY UPSTREAM UT-DS = UNNAMED TRIBUTARY DOWNSTREAM
WARREN COUNTY PCB LANDFILL AREA DIOXIN·RESULTS ALL UNITS IN PARTS PER TRILLION (PPTJ IC-003-LC =ftWL-65 IC-001-LCH f fWL-104 IC-001-GW IC-002-GW [ (lilt I : r:: : I l(ffi$WMf : t: H$QQ1./ J @ : (Q$\Niflt:: /]£¢.Qf\J::Itf J: ll@@HJ[llit DIOXIN ISOMEBS 2,3,7,8-TCDD ND EMPC 0.009 ND 0.013 ND 0.011 ND 1,2,3, 7 ,8-PeCDD ND EMPC 0.011 ND 0.02 ND ND ND 1,2,3,4, 7 ,8-HxCDD ND ND EMPC ND 0.019 ND 0.012 ND 1,2,3,6, 7 ,8-HxCDD ND ND 0.009 ND 0.024 ND 0.017 ND 1,2,3, 7 ,8,9-HxCDD ND ND 0.008 ND 0.026 ND 0.018 ND 1,2,3,4,6, 7,8-HpCDD 28 ND 0.038 ND 0.134 ND EMPC ND 1,2,3,4,6, 7 ,8,9-0CDD EUBAN ISOMEBS 2,3, 7 ,8-TCDF 79 113.3 0.049 ND 0.07 ND 0.065 ND 1,2,3, 7,8-PeCDF 32.8 32.9 0.013 ND 0.047 ND EMPC ND 2, 3,4, 7 ,8-PeCDF 80.8 118.8 0.021 ND 0.043 ND 0.007 ND 1,2,3,4, 7,8-HxCDF 753 1145.2 0.033 ND 0.085 ND 0.07 ND 1,2,3,6, 7,8-HxCDF EMPC 117.2 0.011 ND 0.031 ND 0.02 ND 2,3,4,6, 7 ,8-HxCDF 65.8 101 0.017 ND 0.04 ND 0.037 ND 1,2,3, 7,8,9-HxCDF EMPC EMPC EMPC ND EMPC ND EMPC ND 1,2,3,4,6, 7,8-HpCDF 673 895.8 0.041 ND 0.118 ND 0.099 ND 1,2,3,4, 7,8,9-HpCDF 628 549.1 0.005 ND 0.014 ND ND ND 1,2,3,4,6,7,8,9-0CDF 4630 4207.2 0.061 ND 0.115 ND 0.105 ND ND -NOT DETECTED AT QUANTITION LIMIT FOR METHOD EMPC -COMPOUND MAY BE PRESENT BUT COULD NOT BE QUANITFIED
Metals
Of the eleven metals identified as contaminants of concern for the site, only one was
found at a concentration significantly (2 times) above background in the 6 CLP samples
collected from within the farmland. Mercury was identified at concentrations
significantly elevated above background in both surface soil and subsurface soil. The
range of concentrations for this metal identified in soil within the farmland is ND to 0.14
mg/kg.
The estimated extent of metals concentrations greater than 2 times background in soil
is shown in Figure 3-27. As indicated in this figure, significantly elevated metals
concentrations are found in isolated areas located west of the old FCX warehouse.
3.3.9 DIOXINS/DIBENZOFURANS
As part of this soils investigation task, five additional soil samples were collected for
CLP dioxin/ dibenzofuran analyses (EPA DQO Level IV). These samples were collected
from locations indicating the highest pesticide concentration as a result of the initial
screening by the onsite FASP laboratory. A total of 2 surface soil and 3 subsurface soil
samples were collected from source areas 3, 4, and 5 during the soil investigation task.
The locations of the five dioxin/ dibenzofuran soil samples are shown in Figure 3-28.
The dioxin/ dibenzofuran concentrations measured in these soil samples are summarized
in Table 3-16 .
.: · Of the 26 dioxins/ dibenzofurans isomers analyzed for by the EPA CLP laboratory, all 26 \-!'?-:;: A'"1••
'\} • were identified in the soil samples collected from source areas 3, 4 and 5. The ranges of
., concentrations for the 26 dioxin/dibenzofurans identified in the soil at this source area
,1.
-~~ · are as follows:
3-118
TABLE 3-16 SOIL SAMPLING SUMMARY -DIOXINS/DIBENZOFURANS FCX WASHINGTON SITE WASHINGTON, NORTH CAROLINA CHEMICAL se-11; 5,0 ss-ee SS-131 SB-133 SB-133 SB-134 .0.•-,5• 0'-.5' 1.0' (DUPl 7.5' •-;;,jM;t;iiJ!;IBA¢fl~9.FV>Q(!3.~N.?!PPl9)<lf{ftti /HJ :rtfti~<ft}if !4ie:}/f )flt /J)i})f: ::1 =Ii1ii&i~il~wlgia§.l~tijiai~ii~!l!ti I:@\ ··:;· it@]i:J!':]}:~:11::r:::t:r:r:··::: · '::':·'=( -:,,-::~-,, ... : -:rri ;Jt )('••· .· :-~ -{L} , , :;:loo.itt&F~i#R{§'@.~/ii:Nl~~~*'~!':...... :/:! :~&t=:i]]j:J;;;~){t' ... :. :·, ·:_· ":' .. : ··:·: ··::•::;:~~:: : . :· .. : : =~~:::-·: !lt=?t{:} i:· .. ' .. 1,2,3,0,7,8 HEXACHLORODIBENZODIOXIN 10 0.8 -400 030 .110 iiil~)iii)i.!HtAA§H(i?iji$.~\ijt~#5.p1~xfrf 1% if!':\iJm::::::::: :%:!]i#lf:fl:!IIMlJ]:1r:r=1NJ]l!]l ~9ij\/t%\[U~~)Ill ]i]I HEXACHLORODIBENZODIOXIN (TOTAL) 110 OBJ 2.1J 4700J 0700J 2.IIJ J;J;4;J;~;t;,f ijtef.*-pi@§iitji;liijgiji9.QipxiM! =tittt#.~litt:rrt ::~#fai'[]f ']}b]:!:Jt!/!t:!tAl@&lt ·ttJM@¥:t::f :+t=t ]t=:Jt HEPTACHLORODIBENZODIOXIN (TOTAL) 440J 850J -54000J 83000J :a~tio.Htb.ij#i:iiij!iji.bbfr,#1ri:i't $±id t = ,:=:t ; _:_·_ ···· --: :~ioo::i· :::::-:·'':':'::i2&W''."."''.''.'.:'.:'.='.''·',aeoriJ -.-.,, · ·' ·:·iooi>oo:i·:, ·::--·i,-doooi".i<W?fif't: ,,,,,,,,.,.,., 2,3,7,8 TETRACHLORODIBENZOFURAN 2.3J Ji.fij!4i1UaM:!'.i:iiij~'.tii'.zqif.@AN:ft&fi~>t ''i\~\:~¥:ttiLP!::IH:Jt:tt 1\if;/Ji U=ttt~ijifi:'iJ•t·::rn:JUiiiff ,,:::;,-,,, .......... , ..... " 1,2,3,7,8 PENTACHLORODIBENZOFURAN e.5 15.3 :~;ji◄,i1•ei&r~iij~c:;;~9p1aiijz9.i:~ijiNt:f , ,. ····::::i:a;ij;,;J, .w.w .•• :At. PENTACHLORODIBENZOFURAN (TOTAL) 22J 18J -1110J 1150J JjiliiJd;iBe.i®.f@$ijppfije.f,1il:i/:fiJa~fdLrr : > t::=21e::: :/f!:lifij#Ji'i] :l?lJfitlilif M#:\!f !@ :t:f~ijif!:t•·' ' . :Ai:il!/< :, ·,:,:rt 1,2,3,11,7,8 HEXACHLORODIBENZOFURAN 2.e 1.4 -111 11 :miJ#6~Ji:Ht~mm~ijqpjijMj§€U!!Mt:· 2,3,4,11,7,8 HEXACHLORODIBENZOFURAN 11.1 7.11 . H™[e-mail],;ijiff9f);ttt::t: ,,,= asl.::::J ::u:J!/iji£t!:i:::J1::+ir•:•·'::·•-•:·'· _:,·:=noor _,,, .. : ::tiii#: :::rr:::ri:1::'1r· 1,2,3,4,ll,7,8 HEPTACHLORODIBENZOFURAN 100 33 -740 830 4.3 JM~)!Milif ijijf t*-~ijijqijqpiijtijzqfiJij!ij ::t if]!':]!=] ~)i!l::!t!lfi!f j)j{f !]'f !?l!!§ilf !!f !l]f i!Uttltti!f (J.ij!]t(]=if if i:!;ijijf li:::1:1r:: ;4tiiB'i~ifiij,Lijt.fft~~~ijiij1i'tiit!t:t: -.... ·:· · · !:! t:t::;1rn:t:mtt:m:;1:::fi!:l:]i]}f'!]t!:lt]:t:::;t00:~Ilt::ti;::::: tti':!#10\tlf!tit _;;,! TEQ(TOXIC. EQUIV. VALUE, FROM I_--TEF/811) 14J 11J 3.eJ 7110J 880J .20 NotH: -lndlca•• not detected J lndlca•• Htlmatad value Concentration• prHented In ng/kg ,J
1
-. . f, . . . , r. ·-"...-----------------------------.. -~ ( .v *~ -· ..
~ -N-~
200 0
j,------1
" ~ " "
SCALE IN FEET
LEGEND
-X-FENCE
" ,.:
200
FARMLAND
CHARLIE TOM'S
RESTAURANT & R BAR
W.B. GERARD
S, INC.
~ TREELINE
-··-SURFACE WATER
____ SOURCE AREA
BOUNDARY
@ SOURCE AREA
/~-((
e SURFACE SOIL
SAMPLE LOCATION
O SUBSURFACE SOIL
SAMPLE LOCATION
/
/
COM FEDERAL ARCS IV
DIOXIN/DIBENZOFURAN SOIL SAMPLE LOCATIONS
FCX WASHINGTON SITE
WASHINGTON, NORTH CAROLINA
ESIDENCE
FIGURE NO.
3-28
-" , ...
ii ....
A __ ~-~ ./u~ cf{ c~,v
~k ~~·~ ~ '~J;? ~~?_
d) ~ r~,Jo ~---_,,fl ~
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···-·--•-n----··-.., . ..-.,.. '.;,-.-:!-'($ .. ,( ', ,; :'-·': ~----··. _. -----· .,:.-.;..~#*~. ~ .. ~·-·':!!·•-•-,.-··--... .,._.,...,,... ..... ;··~~-... ------~.------·---·~-..... ----· r·
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al
\Federal Register / Vol. 56, No. 35 / Thursday, Februa1y 21, 1991 / Rules and Reh~lations 7163
~
with an inlet gas lemperature within the
range of 450 to 750 °F, or if it is an
industrial furnace that has hydrocarbon
levels exceeding 20 ppmv. See § 266.104.
Dispersion modeling must be
conducted in conformance with EPA's
"Hazardous Waste Combustion Air
Quality Screening Procedure" provided
in Methods Manual for Compliance with
the BIF Regulations or EPA's Guideline
on Air Quality Models (Revised) which
are incorporated in today's rule as
appendices IX and X, respectively, of
part 266, or "EPA SCREEN Screening
Procedure" as described in Screening
Procedures for Estimating Air Quality
Impact of Stationary Sources. The latter
document is incorporated by reference
in today's final rule at§ 260.11. To
evaluate potential cancer risk from the
congeners, prescribed procedures must
be used to estimate the 2,3,7,8-TCDD
toxicity equivalence of 2,3,7,8-
chlorinated congeners. See "Procedures
for Estimating Toxicity Equivalence of
Chlorinated Dibenzo-p-Dioxin and
Dibenzofuran Congeners" in Methods
Manual for Compliance with the BIF
Regulations incorporated in the rule as
appendix IX of part 266.
Studies conducted by the Agency 40
and others 41 during development of
regulations for municipal waste
combustors (MWCs) concluded that PM
control devices operated at
temperatures greater than 450 °F have
the potential for emitting elevated levels
of CDD/CDF. At these temperatures,
precursor organic materials and chlorine
in the flue gas can be catalyzed by PM
captured in the PM collection device to
form CDD/CDF. Based on these
findings, the Agency proposed to restrict
the combustion of hazardous waste in
BIFs that operate with PM control
device temperatures greater than 450 °F.
A number of commenters opposed the
proposed limitation on the flue gas
temperature to less than 450 °F. Several
commenters pointed out technical
distinctions among types of boilers and
industrial furnaces that affect the ability
of a unit to change flue gas temperature
and the potential of an ESP to form
CDD/CDF. For example, many boiler
and industrial furnaces either combust
wastes that are very low in chlorine or
that have high levels of chlorine capture
within the process (e.g., cement kilns).
•0 See U.S. EPA. 0 Municipal Waste Combu1tion
Study: Combu1tlon Control of Organic Emi11ion1"'.
EPA/530-SW-87--021C. NTIS Order No. PB87-
206090; U.S. EPA. ""Municipal Waite Combustion
Study: Flue Ga■ Cleanins Technology"". EPA/530-
SW-87--021D. NTIS Order No. PB87-208108; and 54
FR 522.51 (December 20, 19811).
• • Vo83 H. and L Stieglitz. ·'Thermal Behavior of
PCDD/PCDF in Fly A■h from Municipal Wa■ le
Incinerator■"'. Chemosphere, pp. 1373-1378, 1986.
As a result, the CDD/CDF emission
potential will vary for different boilers
and industrial furnaces, as well as
between boilers and industrial furnaces
and MWCs. Commenters also stated
that there la no direct evidence of CDD/
CDF emissions from several types of
boilers and industrial furnaces, and that
compliance testing to demonstrate 99.99
percent DRE of POHCs and continuous
monitoring of CO and HC levels is
adequate to ensure minimal emissions of
organic compounds.
The Agency has reviewed the
available data on the theory of COD/
CDF formation as well as CDD/CDF
emissions from BIFs. Based on this
review, the Agency agrees that most, but
not necessarily all, BIFs burning
hazardous waste have low CDD/CDF
emission rates. For example, EPA
recently tested a cement kiln burning
hazardous waste that operates with an
ESP at a temperature of 500--500 •p and
found it to have relatively high COD/
CDF emissions.42 (EPA conducted a risk.
assessment, however, that estimated the
increased lifetime cancer risk to the
hypothetical maximum exposed
individual from the CDD/CDF emissions
ranged from 7 in 10,000,000 to 2 in
1,000,000 without burning hazardous
waste and from 2 in 1,000,000 to 4 in
1,000,000 when burning hazardous
waste, well unde,: the 1 in 100,000 limit
established in today's rule.) The Agency
suspects that the elevated CDD/CDF
concentrations in the stack gas at this
cement kiln are the result of the ESP's
operating temperature and the level of
HC precursor material in the flue gas.
HC concentrations ranged from 66 to 70
ppmv (measured with a hot system,
reported as propane, and corrected to
7% oxygen, dry basis) without
hazardous waste burning and from 38
ppmv to 63 ppmv with hazardous waste
burning. (We note that to continue
burning hazarpous waste under today's
rule, the Director must establish during
the part B permit proceedings an
alternative HC level for this kiln based
one demonstration by the applicant that
HC levels are not higher when burning
hazardous waste than under normal
conditions and that the facility is
designed and operated to minimize HC
emissions from all sources-fuels and
raw materials. At certification of
compliance with the emissions controls
other than the HC limit, this facility
must also propose a HC concentration
limit for the remainder of interim status
(until that limit or another limit is
established under permit proceedings)
u U.S. EPA. Emi11ion■ Te■tins of• We! Cement
Kiln al Hannibal. MO, December 1990. ' ·
that will ensure that HC levels when
hazardous waste is burned will not be
higher than baseline levels (i.e., HC
levels when the system is designed and
operated to minimize HC emissions from
all sources, when burning normal fuels
and feeding normal raw materials lo
produce normal products, and when not
burning hazardous waste).) In addition,
trial burn emissions testing must
demonstrate that emissions of organic
compounds are not likely to result in an
increased lifetime cancer risk to the
hypothetical maximum exposed
individual exceeding 1 in 100,000. See
I 266.104(f) and discussion in section
11.B.4.b of part thre~ of this preamble.)
There may be other factors that
influence CDD/CDF levels at this
facility (and other facilities), but this is
uncertain. In addition, the exact HC
concentration in combustion gas below
which elevated CDD/CDF
concentrations will not occur is
unknown.
The Agency continues to believe that
the operating temperature of the PM
control device (and HC concentrations
in flue gas) plays a significant role in
CDD/CDF emissions. For a given HC
concentration in the flue gas, the
available data suggest that the potential
for elevated CDD/CDF emissions is low
if the PM control device operates at
temperatures of less than 450 •p or
above 750 °F. Consequently, today's rule
does not require BIFs with PM control
devices operating at temperatures
outside of the 450-750 °F window to
determine CDD/CDF emission rates
(unless it is an industrial furnace with
HC levels greater than 20 ppmv).
Owners and operators of units operating
within the temperature window,
however, are required to conduct stack
testing to determine CDD/CDF emission
rates and to conduct a risk assessment
using prescribed procedures to
demonstrate that the estimated
increased lifetime cancer risk to the
hypothetical maximum exposed
individual is less than 1 in 100,000.
The Agency notes that the final rule
municipal waste combustors (MWCs)
may take a slightly different approach to
control dioxin and furans by limiting
temperature, at the inlet of the PM air
pollution control system to within 30 °F
of those achieved in a dioxin/furan
compliance test. The preamble to that
rule, however, will probably continue to
note the possibility of dioxin/furan
formatiQO in the temperature range of
230 ·c (450 °F). In today's rule, the
Agency believes that using temperature
and HC levels as a trigger to dioxin/
furan testing and risk assessment will be
fully protective of human health and the
(
I • .. 7164 'Federal Register/ Vol. 56, No. 95 .Y Timrsday, February 21, 19M J Rules lltld Regula:tions
environment and somewhat easier 1o
implement than tbe MW'C approach.
Ill. Risk Assessment Procedures
The Agency uses assessmen't ofnealth
ri sk 1o develop and 'imp1ement the final
rules for me'tals, hydrochloric acid '(HCl),
and chlorine gas (Cl2). -Specifically, 'fhe
Agency has used risk a11Bessment to: (1)
Establish ambient air concentrations m
appendix VIII compounds ·that do nol
pose an unacceptable health risk for
purposes ·of this rulemaking; and (2)
establish risk-based, conservative feed
rate ·and emissions Screening Limits for
metals •and HCl. ln "Bddition, if facilities
fail the Screening Llmits or elecit to
conduct dispersion modeling to obtain
less conservative limits, 'fhe rule allows
facilities to use site-specific di9Persion
modeling 1o e&tablish emisBiun 1linrits,
and ultimately feed Tim! imnits for metals
and chlorine.
To establish health-based ·acceptable
ambient concentrations for
nonoarcinogenic tmdc .metal and
nonmetal -compounds (eKoept for HCI,
C'2 and lead), -EPA -converted oral
reference-doses ·to -reference air
concentrations-(RACs) by•assunring
average breathing volumes and body
weights, and by applying.a &afety:and.a
background levelfactor. See·54 FR at
43756. Health,based .cnncentrations -for
carcinogenic ·pollutants Mere derived-~
converting cancer .potency factors, -or
slopes {unique for each·C8l'cinogen), into
Risk Specific Doses fRSDBt) .at a risk
level of 1 in 100,000.43 Since oorcinogena
are assumed to pose a M1all but finite
risk .of .cancer even at vecy low doses,
the RSD reflects .a .cen\ain risk level,
corresponding .to .1 chance in 100,000, or
10-• excess risk of cancer for fhe
maximally.exposed individual if
exposed continuously to.multiple
carcinogenic chemicalsJor a 70-year
lifetime. RACs for HCt and Cls are
based on inbalation data. and a RAC for
lead is ,based on the National Ambient
Air Quality Standard {NAAQS).
To establish the Screening Limits far
metals and HCl, air dispersion modeling
was applied to'back-milcula1e maximum
acceptable'feed rates and stack
emissions rates from.risk~irased,
acceptlible ambient concentrations.
These -calculations were,penormed for
various terrain types, effective stack
heights, and land use t:lassificaticms.
The Te stilting -permissrHle · Screening
Lirrifts Teflect .plausib1e, -reasona'ble
0 We note that the cancer rialt from.the
carclnogerilc llll!tal1 mull be 11111Ullett to ensure ftutt
the eummea riik ·ta;not 11n1•ter then l 'in '100(800.
Thus, whenmon, than'1ffl11~ mellilil1 -.
emitted..the allowable wound level oolltlllntrall•
for each carclnogealc metal ls Jes■ than the 10-•
Risk Specific Do■eforthllt ml!ldl.
worst-case assnmplions about a genetic
facflity that are not site0 specific:The
Screening Limits ·process provides a
rapid and -converiient-risk•based
mechanism to ·determine cc,mpliance.
Conservative essump1ions 11sed to
estimate'hea'lth impactil e,cposnre in the
Screening Lirrift process include: ;(1Jl:Jse
of reesona'ble, ·worst-case esfhna'te elf
di11persion df stack -emissions; ·and(2)
for the Tier •I feeil rate Screening Limits,
'assuming that ell metals and chlorine
fed into the BIF in all feedstreams 1tre
emitted fi:e., there is no partitioning to
bottom ash or product, :and :not l'emov11l
by en air.pollution control·.syirtem.44'See
52 FR 17002 (Mey '8, 1987) and 54 PR
,1S729 {October 26, 1989). Thus.
assumptions '8.Jld ·the Screening Limits
tend to CIT intentionally on the aide of
protecting lnmum health. 0
If-emission levels -exceed -the
Screening ·Lhnits (or:.if!the,owner/
operator so eleats), ,the•mle allows ·a
facfllty'te .cmtduct ,Its 'Own 1Jite--specific
air dispersion modaling tn•order le
e1rtitblieb -metals, HG!, and Cls emisaie,11
limits. Incorporation of•ite-epecific
information allows lees ,conservative
asswnptiom (than !the reasonable wor.et-
case, noneite-epecmc tlefamteJ .to 'l>e
used in the -diepereion m<Klels.
Consequent!'-Bite-specific air
dispersion modeling mav pr.edict ·lower
ambient·concenb'atiEJll&•than 1he
nenaite-specific modeling reflected-in
the Screening Limits, thus allowing
higher emiHiona and :feed .r-ate ,limits.
A. Health 'Bf!er:Jts Data
1. Carcinogen&
Heelfh ~fects •evalmrtions .for
carcinogens •have 'been summar'Pzed in
Pat.t'Three, I. 0, "Bvlfhra1iffl'l elf llle«lth
Risk" in the April ·27, '1900pop0111il 1sire
55 FR 1-7873). To 'Summurlze briefly, in
contrast :to nom:arclnogem1, ·carcinogens
are as1111DJed tm tpresent a 1ITT1a1J llmt finite
rhik 'Ii£ !CBUliing cam::er, ,even.a't very 'low
dases. '1'be !ilope ufihe dDBe•response
curve in 1he low duse:resian :bl assumed
to be tinear !for -clffliirmgans. &!cause ·of
.,. 'Po·dbtalln credltTor partlffomnw'19 t'ft91due er
product and for-A:l'CS NIIIIOftl'11ffluianay.cOWtmn
and operalDrunu&t .conduct eminlona te■ting to
demonstrate !he overall 'S_y•tem Removal Efficiency
(SRBJ-,,artltlorilD!J plul AP'CS·l'BIIIOYal efficiency.
TheAgBnq,1um·ncrt.llnllJlled an SRE<ln<tleveloping
the Tier I feed 1N1te&n!en1Jia Llmi■!beoauee-th­
arellll8JW .alte-apeciflc factom.tbat·can.affectrthe
SRE.
•• Wenate-thllt·fhe Scnientng Llntlb may not
al-,-!be•-•thre, lmw .... 'lfoda;i. nlle
ldentlfle1 crileril whereby-tbe'9mN11b11?lmit111111•
not be und ._ llll!y.~y.aot:bemna_atl,,._
See I 266.l06(l!). -niat,p81'Q111_ph, In Iha nile alao
gives the f\gency-nthority to ~fm·whether
the Screening Umlt1 may not be protective In •
particular 1llwltlon. In that case. the.owner and
operator muet uae .the :t'ier m.prooetlu---.1te-
1peclflc dlepenilon mottellng.
this, the slope ofthe curve in 1h-e low
dose re_gion may be-used as an .estimate
of carcinogenic _potency. The unit risk is
defined as tbe "incremental lifetime risk
estimated lo resul't from e:i<;posure o1 an
individual for a 70-year lifetime lo a
carcinogen :in air containing 1 microgram
of the compound per cubic.meter of air
lµglm '). Allm air concentration of :l µgJ
m', the cancer potency elope is
numerically equivalent to the uriit.rlsk.
Thus, at a preselected risk level. the
corresponding air concentration wbich
would cause that risk may be calctilated
by .div'idiqg -fhe desired risk level by the
unit.risk value. Although the resulting
value .represents an air concentration
witb units,of_f,L8/m', this concentration
is .referrea io,as 1he Risk Specific Dose
(RSD).
When exposed to·more than one
carcinogen, ·the Guidelines for
Caroinogenic Riek Ailtlessment ,(St FR
33992 jSeptember 24, 1986}) ,recommend
adding mk11 hmn ,fue individuid
caPCinogens ,to 'Obtain the 8!8l'~ete ,risk
(i.e., cancer risb-frem ,e:,qposu,e te -more
than ,one ,caroirn>gen -are assumed ,to ·be
additive). For today's-r.ule,·the Agency
hm, 'Jl?8;J)t}Sed ,that. en BlJ81'f!B&le risk
level for metals (i.e., -arsenic, beryllium,
cadmium, and ,hexavalent ,chromiwn-) ·of
to-6 is-appropriate bemuse iit w.ould
limit the risk level •for indiwdual
carcim,gens1o therorderof u-•. The
Agency p>int&,out. •however, <that in
selectiQI the -epprymate Tisk 11!1\le1 ifor a
particular,resuletoey :propun, it
cCJDBiders •auch ,faotol"B ,as ,the parfioular
sta1utoi:y mand&te invcllved, nature :of
the pollutants, control -altema'tires, fate
and ,transport-of 1he ,pollutant in
diffeJeDt media, and potential human
exposure. See, ,e.,i., r54 flt at .38049 {Sept.
11, ~ Panicular factors -bearing on
the Alency'a dimoe -here include :the
wide array and potentially ilarge
volumes c:if uarcinogenlc pollutants ;that
can be•eniitted hr these -devices 1funlike
the :al tua tion ln snob irules ;g ,the
benzene :N£-sllAP when• 1ringle
pollutant with ·weH"1Ullieratood ,effects
was attisBW!l),llhe need teigwm:liapinst
envinmmen:tal-harm:n -well BB :harm !tc,
human .health. 1p1>kmtial 9}'118lFfflC
effeota al the ca1'CinlWID9 mnitted ,by
dreee dewces 'tw}iich •effects ,are not
ecoemrted for by .the risk assesament'},
and legislative history indicating
Congressional-preference forparicy of
regula~n between IBIFs humiDg
hazaNknas wa-ste fuelumd -hazartfoue
wmrte bu:ine11ttott1 '(B.·fttu,.:No..284, "!fflfh
CoQg. '1.al Sesa. ,38D. 1n Jlaaman, ,fue
increased recognilum el lhe!lle8d to
cantmhiet:eiriemimmni ~1uKic
polll1hmts :genera1ly, '!llani'fes't'in Tttle m
of the 'Clean Air 1\ct 1\menaments of
t I
7162 Federal Regialer J Vol. BG. No. :35 .I 11hm:sda}l. :Paruary '.21, 1991 / Rules ena 'Re_gula'fions
indication ·of.oombuslion conditions
than is possible with an NMOC -monitor.
Hot Versus Cold HC Monitoring
Systems. Except as indicated below, the
final rule requires the •usenf a hot or
unconditioneil HC monitotiQg system
that must be maintained at.a
temperature of at.least 150 •c.until ·the
sample.gas exits the detector. See
performanoe specificatiollfl in Methods
Manual for Compliance wilh ihe BIF
Regulations (incorpornted in today's rule
as appendix IX of p art 26~). Given,
however, that the tecbndlogy has just
recently been demonstrated n to be
con tinuou~ly opera tiona'I ·on ho,:ardous
wm,te combustion devices, ·the final rule
ailows the use of a coudltioned g11s
monitoring system during the Initial
phase of intr.rirn status operations.
Facilities in interim sta'tus 1hat certffy
complionce w?th •fhe emission standards
for metals, 'HCI, Cl2, parttctilate matter,
00 and HC wrthin•rnmontbs of
promti1gs1ion of the 'fi.r.al rule may use a
conditioned ·gos system. 'Facilities that
elect·to obtain ·the automatic 12-month
extension Tm-·a ·case:by,case extr.nsion)
,Jf the 18-monfh certificirtiun d!)aciline,
hO\•vever, mny net use a condrtioned gas
system because fbe ull/:litional time
provided by fhe-extension-.;iil also
provide 'fime 'to install ·fin -uncondi!ioned
I IC mon]loring-eyrrtem. Thetie .facilities
must demonstrate complhmce wi'fh ·the
HC limit 11sing an unoonditionerl gos
monitoring system. ·Fnrfher, facilities
thnt certify initial domplianoe .miing a
conditioned gus (cold) eygtem mmtt use
an unconditioned -gas fhdt)·11y11tmn when
!her, Tecertifr, compliance within :three
years of -certifying faltial :oomp1iimce.
EPA ineqtii.ring the use-of a hot
monitoring '!lystem becauee itt ,repretmnts
best demomtr11ted 1echnology•Riven 1hat
a I urger fraction -of :HC emiBJiimni can lbe
detected with •a bot :&y9tem. A,
di~cussed lit proposal, 11 hm HC
monitoring S\fB!em ,can detect ll
sub!!lantially larger fraotia uf
hydr(')carbon ·emiseione !than ,111 lfflJld
system. This le ·because tile 'Cfllrl By.Stem
uses a g11'I conditioning sy,tem tturt
removes semi-and nonvo1alil£
hydrocarbons and a 11ubtttamia't fraction ·
of water-so'luble valatile hydrocarbons.
EPA .received numemwi.orunmenle
regarding,gas cgnditioni~-{heated
versus unheated) for HC··monitoring.
Eight comm enters .are m .fMrer of-gas
conditioning. T.he ,pu.rpoe.e of:88'5
• • Entropy !Bmllnmsnet1htl Jnc.. "'IEualuatlon ·of
heated 'IHC Monitoring StY•tema fer.'llanrilom
Waste lnolne1ator EmiulonMeUUtMllent", Draft
Final Report, Octdber 1990;.anll Sbamat..Nai1lm. el
al., "Total ffyllreceibon Analynr'91ultj~. ·P,g,er
presented 11t.lhe'.tlllnl Water~ Corrtrdl
Federation Conference in ,Waeli~.OC. Octot-
8, 1990.
conditiorrintris ito TmnDve IDIDistme from
the -combustion 'J!B'BeB itbat can degrade
instruments m plug •sample lines.
Sample ,oonllitiOilllJ8, ihowe.ver, -can irlso
remove ,wome of fhe wmer:1rdht1,re
hydrocarbons rand the lll'Bllli-:and
nonvolafile bydrocerbOIUJiin-the flue ga11
such thntmethane end.uther
nonhazBJ'dons vohrtlle ·h1drocarbons a,e
frequentliy ·fhe dominant oonstltuertte
measured ·by the detector. ·.Some
commenters were concerned !ttmt fewer
PICs would be detected bf a
conditioned ·(-i:e., cooled) monitoring
system. However, one,:;ommenter:atatell
that-even ·thou!Jh the conBtituents
contributing-most of the hyptttheticel
risk are relatively nonvolrnle they are
relati:vely nondetm:teble 1hnmgh ·an
unconditioned ,theated:) monttoring
system 'because ·of theidm lngen t:onterrt.
,As di9cuseed ,at pmpcunll. ihe Agency
is usin8 HC monitflring to 1implement 'the
teohnology-based HC ·limit oUO ppmv
as an -indice-tar of good 1JOmbustion
conditions. The HC ·monftor1is-mrt :nsed
in an lfttempt to quantify•organic
emissions for·riek -assessment :purpusea.
Emissians testi118 hes shown .that tlmin8
combusti«m upset conditione, -bath the
hot end cold HC monitming sylttems
detect an ·Increase ·in ·HC ,levels ,becatIBe
under upset conditions there Is a
substantial tncrense in hytlrocarbon
compounds that ll!'e readily ,detected by
eifuer monitoring system.n
One commenler!BU8St!Bted·tmrt, :r&fher
than specifying a -range uf ~ · "F for
operation rm -the t:anditioner aw
proposed, a epeci1it: 'COilditioning
temperature 152 "F1) ,ahmild he nquired
to preclse}y ·de'fine 1:he c:mntitii:ni.,d
Mmplm,:procedure. We•agreeTthat a
minimum temperature !Should he
epecilfi.ed •rather -than 1he :range. The fill1lil
nrle allows a t:andtt:ioned monitari.ns
system dllmll! the Initial l}hne of
Interim status, 1111d ,eqmres that1he
sample gas tempenrture mmrt be
maintained et ·a minimum of CO ·•F at B'tl
times prior '.lo dmcharge fmra tthe
detector. EPA 11elm::ted a ·minimum
temperahme,ef•.O "!Fifrom 1he-rengeiafa
to.&4 ~F ,tc,emwe that:moisture was
effective!J, :n,moveil ifrom •the 1JBS wamJ:fle
to predlude plugging .and !fouling
prolilems 'Witta the'DlOn!tcniiDR sy•tem.
Three a,1rm1enleni :111J881!Sted ·that the
HC limit oUS ppmv be n,-e,amitnell
becauee ~• trondi:timiing temperature■
or dther~ in thc4116&91Btilileilt
111BPl'\ le ·req~ -the ·on dh iiat.
uncondltlmuidlHC·IIIDliltoriJll-,ne•'feetcepl,uniJer
certain clrc\lJMlaa-•durtnsfte•butial1phae:of
lnlarim•tatu-i becauu hot~.--.
nonl!tlu!le11. mom conunraUve In that Ibey detect a
larprlfRiotlon-df·11rpnlc1fflTIIJIOUlril'ln ,nniulom.
Further, houy.iema mpNNIII INetcdnioutNlell
, tel!malllllf .for monitom,c,HC lnela.
method may ·lrifluence :the amount of HC
irneasurea. !Given ·thirt the 28 ppmv 'limit
Is 'based prlmarlly on test ~um ·data
ue1ng 'heatea 1i!B., uncandllioned)
monitoring systems, Ote Agency
com,idered 'lowering ·Ote 26 m,mv limit
when a cold (i.e., ·conditioned')
monltoring l!Ylrtmn is-used. _(Limited field
'test data indicate flurt ll hl!ated s_ys'tem
wotild detect from 30% :to '400% more -of
the nra&B of organic compounds ·than a
conditioned i,ystem.) We believe,
however, that fue 20 ppmv TIC limit is
ittfil appropriate when a conditioned
system is nsed because: (l) 'J'he data
correlirtlng.heated .vs corrdifioned
systems are verr limited: (Z) the data on
HC emissions are1imtted (and there
apparentlf Is confusion in some caees as
to whether the data were ·taken wilh a
conditionea or uncondilianea
moriltor1ng system): and (3) fue Agency's
risk methodology is-not sophisticated
enough to demonstrate .that .a HC limit
ofo or lOppmv,using .a conditioned
eyetem rather !han an unconditioned
eylitem ,is needed to protect human
health 811.i the environment 'llhe .SAB 38
also concurs with fuis :view .. (More
detailed responses to .comments.on this
issue are found in a separate
baclcground -document;)
E. Control of Dioxin and Furon
Emissions
For faoilitie1 thatmayJtave the
potential •for ¥ifioant •emiesicnt11,of
chlomieted -di~nzodirocine ,anu
dibemofumn11 .(Clll)/0Df1, the final ,rule
requires iemiffime ,teetin1 ,for both
Interim ot1\atus end •new f&cllities <to
detemnine·emisirums,rates of ell itette-
octa congeners, calculation of a tamctty
equh,alencr, fador, 11!Id-dispersian
medelinsito,demcmlftrate'that fhe
predicted ma:,rimmn 11D11ual average
gmund ·level ·concentnrti..ml 'ti.-e~ 1he
hypofllelical mmmnum~pnsed
lndivilhml) does mrl eo:eeil 111!'11!!11 1ha t
WNld reBUU •in ,an 'incn,aaed lifetime
cancer risk of more than 1. ln 100,1JOO. n
The ~ cmmidel!S .11 faoili~ ,o .have
the !J)Otmrtbil iourigrdficant ODD fCDF
emiseions·if ttiis ffllUi.PJ18d wtlh,a,dry ·
pal!titnilate-im1tteu1ontro1 dev:ioe fe,g.,
fabric iii Im or ll!leuttwla1ic,PJ9Ciplta tor)
nv.s. '1D"A. "'Report df•the Prottm:ta oT
lncomph!lelOcmtbu•tton'ldt-nnltttMI oHhe
Sele~ Adviaaiy-lloanl",«.lll # fll'A-a&AB-BC-
80--004, lan~ .l'IIIIO.
11 EPA u aol toqlUJU18.dial,tho.ealimatea cancer
risk from CDI)/CDF'be a84ea to .the n■lt from metal
enlleai«w tu'llumontrll'ate IIMft the-.ummeft mk1o
the muhnum•acpmod'tndbltdualilalleN lb■n 111 ....
The A,em:y,Nlie-that lU■ m1111'f'1:1Priate to-
the,e1timotedJiealth.ruk from -.la thatAre
known or prdballle liuman carclllogena wllh a
toxlclty eqliinlenc:y·factor for CDI:t/CDF lbat'la
d.tpad11D-YIIII' -afi,oe.
..
State of North Carolina
Department of Environment,
Health and Natural Resources
State Center for Health & Environmental Statistics
James 8. Hunt, Jr., Governor
Jonathan 8. Howes, Secretary
Delton Atkinson, Director
To: Sharon Rodgers, DSWM
From: David Vogt, Environmental Statistics, SCHES
3/10/95
Subject: Statistical Recommendations for Sampling Dioxin at Warren County
Landfill
As requested, I am providing you with a write-up of my recommendations
in conjunction with our recent meeting regarding dioxin sampling at the
Warren County Landfill. Please keep in mind that the following are technical
(statistical) recommendations and may or may not be acceptable from a cost-
wise or policy standpoint.
Statistical Methods
• My recommendation is to use nonparametric statistics for two reasons:
1) Sampling of environmental "pollution" usually produces data that
are not normally distributed, but are right-skewed. Parametric
methods (mean, standard deviation, t-tests, etc.) assume normal
distribution. Therefore, I propose that a distribution-free test such as
the Wilcoxin Rank Sum Test (comparing 2 sets of data) or the Kruskal-
Wallis Test (comparing more than 2 sets of data) be used.
2) The above tests can accommodate a limited number of non-detects,
which are highly probable owing to the nature of the contaminant that
is being sampled.
Sampling Design
I realize that laboratory analysis of dioxin is expensive and hence have
designed the sampling protocol accordingly. However, please realize that
if you want the analysis to be statistically defensible, then there needs to be
a minimum amount of samples in order to carry out testing of the data.
I recommend sampling the outlying private wells in quadrants that
match the locations of the monitoring wells immediately outside the
perimeter of the landfill (#s 1,2,3, and 4 -see diagram on next page). For
each quadrant, sampling would be spread out to adequately represent
private wells throughout that quadrant. Sampling variables such as the
P.O. Box 29538, Raleigh, North Carolina 27626-0538 Telephone [phone] FAX [phone]
An Equal Opportunity Affirmative Action Employer 50% recycled/ l 0% post-consumer paper
distance from the landfill, well locations, well types, well depths, etc.
should be determined by a hydogeologist.
I recommend the following number of samples: 6 for each quadrant, 3
for each perimeter monitoring well, and 6 for the monitoring well on top
of the landfill (#0). For the perimeter and landfill monitoring wells, it
probably would be best to take samples at different depths if possible.
Depending on how fast the laboratory can process the samples, the
sampling schedule should be staggered. For example, sampling frequency
could be every third day at 2 locations in each quadrant (spread out), 1 from
each perimeter monitoring well, and 2 (at different depths) from the
landfill monitoring well. This would amount to three different sampling
days.
Key:□
Landfill
I
III
•
Existing
Monitoring Wells
N
II
It is important to understand that if the samples produce a lot of non-
detects, then statistical testing will not be advisable (the tests mentioned can
handle around 10% non-detects). If there are samples that show detectable
levels of dioxin only in one geographical area, then perhaps additional samples
should be taken at locations staggered within that area. However, if this
scenario occurs, it would be best if a hydogeologist first estimated the extent
(plume) and direction of flow of the groundwater in that area before additional
sampling was performed.
Finally, before sampling commences, it might be worth the money to test
the sampling equipment and lab facilities by running the procedure using a few
blanks. At the highly-sensitive level of detection you described, parts per
quadrillion, it seems to me that it would be prudent to first check for any type
of possible equipment contamination.
Please feel free to contact me at 715-4474 if you have any questions.
cc: Paul Buescher
Delton Atkinson
., a"i'ion of Toxic Organic Compounds in Air BC Factot • AB lculatlon: I I 0 1ht • DE • 100 mm 1 HalQht • BO • 10 mm 1h It 10% PHk HalQht • AC • 23 mm 11 mm • 12 mm 12 ,aymmetry Fectot • 11 • 1. 1 Fk?~t ~~ '01~~ f\ ll'~bti-~ Mt~ METHOD T09 DETERMINATION OF POL YCHLORINATED DIBENZO-p-DIOXINS (PCDDs) IN AMBIENT AIR USING HIGH-RESOLUTION GAS CHROMATOGRAPHY/HIGH-RESOLUTION MASS SPECTROMETRY (HRGC/HRMS) l. Scope Revision 1.1 June, 1988 1.1 This document describes a method for the determination of polychlorinated dibenzo-p-dioxins (PCDDs) in ambient air. In particular, the following PCDDs have been evaluated in the laboratory utilizing this method: • 1,2,3,4-tetrachlorodibenzo-p-dioxin (l,2,3,4-TCDD) • 1,2,3,4,7,8-hexachlorodibenzo-p-dioxin (l,2,3,4,7,8-HxCDD) • Octachlorodibenzo-p-dioxin (OCDD) • 2,3,7,8-Tetrachlorodibenzo-p-dioxin (2,3,7,B-TCDD) The method consists of sampling ambient air via an inlet filter followed by a cartridge (filled with polyurethane foam) and analysis of the sample using high-resolution gas chromatography/ high-resolution mass spectrometry (HRGC/HRMS). Original laboratory studies have indicated that the use of polyurethane foam (PUF) or silica gel in the sampler will give equal efficiencies for retain-ing PCDD/PCDF isomers; i.e., the median retention efficiencies for the PCDD isomers ranged from 67 to 124 percent with PUF and from 47 to 133 percent with silica gel. Silica gel, however, produced lower levels of background interferences than PUF. The detection limits were, therefore, approximately four times lower for tetrachlorinated isomers and ten times lower for hexachlorinated isomers when using silica gel as the adsorbent. The difference in detection limit was approximately a factor of two for the octachlorinated isomers. However, due to variable recovery and extensive cleanup required with silica gel, the K ASYMMETRY CALCULATION / method has been written using PUF as the adsorbent. 1.2 With careful attention to reagent purity and other factors, the method can detect PCDDs in filtered air at levels below 1-5 pg/m3*. *Lowest levels for .. hlch the ••thod has been v•lldated. Up to an order of aegnttude betttr sensitivity 1hould be achtev■blt with 24·hour air a ■1nplt1.
222 Methods for Determination of Toxic Organic Compounds in Air 2. I .3 Average recoveries ranged from 68 percent to 140 percent in laboratory evaluations of the method sampling ultrapure filtered air. Percentage recoveries and sensitivities obtainable for ambient air samples have not been detennined. Applicable Documents 2.1 ASTM Standards 2.1.1 Method 01356 -Definitions of Tenns Relating to Atmospheric Sampling and Analysis. 2.1.2 Method E260 -Recommended Practice for General Gas Chro-matography Procedures. 2.1.3 Method E355 -Practice for Gas Chromatography Tenns and Relationships. 2.2 EPA Documents 2.2.l Quality Assurance Handbook for Air Pollution Measurement Systems, Volume II -"Ambient Air Specific Methods," Section 2.2 -"Reference Method for the Detennination of Suspended Particulates in the Atmosphere," Revision 1, July, 1979, EPA-600/4-77-027A. 2.2.2. Protocol for the Analysis of 2,3,7,8-Tetrachlorodibenzo-p-Dioxin by High Resolution Gas Chromatography-High Resolution Mass Spectrometry, U.S. Environmental Protection Agency, January, 1986, EPA-600/4-86-004. 2.2.3 Evaluation of an EPA High Volume Air Sampler for Polychlori-nated Dibenzo-p-dioxins and Polychlorinated Dibenzo-furans, undated report by Sattel le under Contract 68-02-4127, Project Officers Robert G. Lewis and Nancy K. Wilson, U.S. Environmental Protection Agency, EMSL, Research Triangle Park, North Carolina. 2.2.4 Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air, U.S. Environmental Protection Agency, April, 1984, 600/4-84-041. 2.2.5 Technical Assistance Document for Sampling and Analysis of Toxic Organic Compounds in Ambient Air, U.S. Environmental Protection Agency, June, 1983, EPA-600/4-83-027. / Method T09 223 2.3 Other Documents 2.3.l General Metal Works Operating Procedures for Model PS-1 Sampler, General Metal Works, Inc., Village of Cleves, Ohio. 2.3.2 Chicago Air Quality: PCB Air Monitoring Plan, Phase 2, Illinois Environmental Protection Agency, Division of Air Pollution Control, April, 1986, IEPA/APC/86-011. 3. Summary of Method 3.1 Filters and adsorbent cartridges (containing PUF) are cleaned in solvents and vacuum-dried. The filters and adsorbent cartridges are stored in screw-capped jars wrapped in aluminum foil (or otherwise protected from light) before careful installation on a modified high volume sampler. 3.2 Approximately 325 m3 of ambient air ls drawn through a cartridge on a calibrated General Metal Works Model PS-1 Sampler, or equi-valent (breakthrough has not been shown to be a problem with sampling volumes of 325 m3). 3.3 The amount of air sampled through the adsorbent cartridge is recorded, and the cartridge is placed in an appropriately labeled container and shipped along with blank adsorbent cartridges to the analytical laboratory for analysis. 3.4 lhe filters and PUF adsorbent cartridge are extracted together with benzene. The extract is concentrated, diluted with hexane, and cleaned up using column chromatography. 3.5 The High-Resolution Gas Chromatography/High-Resolution Mass Spect-rometry (HRGC/HRMS) system is verified to be operating properly and is calibrated with five concentration calibration solutions, each analyzed in triplicate. 3.6 A preliminary analysis of a sample of the extract is perfonned to check the system performance and to ensure that the samples are within the calibration range of the instrument. If necessary, recalibrate the instrument, adjust the amount of the sample injected, adjust the calibration solution concentration, and adjust the data processing system to reflect observed retention times, etc.
224 Methods for Determination of Toxic Organic Compounds in Air 3.7 The samples and the blanks are analyzed by HRGC/HRMS and the results are used (along with the amount of air sampled) to calculate the concentrations of polychlorinated dioxins in ambient air, 4. Significance 4.1 Polychlorinated dibenzo-p-dioxins (PCDDs) are extremely toxic. They are carcinogenic and are of major environmental concern. Certain isomers, for example, 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-Tf.DD), have LOSO values in the parts-per-tril-lion range for some animal species. Major sources of these compounds have been commercial processes involving polychlorinated phenols and polychlorinated biphenyls (PCBs). Recently, however, combustion sources have been shown to emit polychlorinated dibenzo-p-dioxin (PCDD), including the open-flame combustion of wood containing chlorophenol wood preservatives, and emissions from burning transformers and/or capacitors that contain PCBs and chlorobenzenes. 4.2 Several documents have been published which describe sampling and analytical approaches for PCDDs, as outlined in Section 2.2. The attractive features of these methods have been combined in this procedure. This method has not been validated in its final form, and, therefore, one must use caution when employing it for specific applications. 4.3 The relatively low level of PCDDs in the environment requires the use of high volume sampling techniques to acquire sufficient samples for analysis. However, the volatility of PCDDs prevents efficient collection on filter media. Consequently, this method utilizes both a filter and a PUF backup cartridge which provides for efficient collection of most PCDDs. 5. / 6. Method T09 225 Definitions Definitions used in this document and in any user-prepared standard operating procedures (SOPs) should be consistent with ASTM Methods D1356 and E355 (Sections 2.1.1 and 2.1.3). All abbreviations and symbols within this document are defined the first time they are used. Interferences 6.1 Chemicals that elute from the gas chromatographic (GC) column within .,:10 scans of the standards or compounds of interest and which produce, within the retention time windows, ions with any mass-to-charge (m/e) ratios close enough to those of the ion fragments used to detect or quantify the analyte compounds are potential interferences. Most frequently encountered potential interferences are other sample components that are extracted along with PCDDs, e.g., polychlorinated biphenyls (PCBs), metho-xybiphenyls, chlorinated hydroxydiphenylethers, chlorinated naph-thalenes, ODE, DDT, etc. The actual incidence of interference by these compounds also depends upon relative concentrations, mass spectrometric resolution, and chromatographic conditions. Because very low levels of PCDDs must be measured, the elimina-tion of interferences is essential. High-purity reagents and solvents must be used and all equipment must be scrupulously cleaned. Laboratory reagent blanks must be analyzed to demon-strate absence of contamination that would interfere with the measurements. Column chromatographic procedures are used to remove some coextracted sample components; these procedures must be performed carefully to minimize loss of analyte compounds during attempts to increase their concentration relative to other sample components. 6.2 In addition to chemical interferences, inaccurate measurements could occur if PCDDs are retained on particulate matter, the filter, or PUF adsorbent cartridge, or are chemically changed during sampling and storage in ways that are not accurately measured by adding isotopically labeled spikes to the samples.
226 Methods for Determination of Toxic Organic Compounds in Air 7. 6.3 The system cannot separately quantify gaseous PCDDs and parti-culate PCDDs because the material may be lost from the filter by volatilization after collection and may be transferred to the absorbent cartridge. Gaseous PCDDs may also be adsorbed on Particulate matter on the filter. Apparatus 7.1 General Metal Works (GMW) Model PS-I Sampler. 7.2 At least two Model PS-1 sample cartridges and filters per PS-1 S~mpler. 7.3 Calibrated GMW Model 40 calibrator. 7.4 High-Resolution Gas Chromatograph/High-Resolution Mass Spectrometer/Data System (HRGC/HRMS/DS) 7.4.1 The GC must be equipped for temperature programming, and all required accessories must be available, including syringes, gases, and a capillary column. The GC injection port must be designed for capillary columns. The use of splitless injection techniques is recommended. On-column injection techniques can be used but they may severely reduce column lifetime for nonchemically bonded columns. In this protocol, a 2-ul inject ion volume is used consistently. With some GC injection ports, however, 1-ul injections may produce some improvement in precision and chromatographic separation. A 1-ul injection volume may be used if adequate sensitivity and precision can be achieved. [NOTE: If 1 ul is used as the injection volume, the injection volumes for all extracts, blanks, calibration solutions and performance check samples must be 1 ul.) 7.4.2 Gas Chromatograph-Mass Spectrometer Interface. The gas chromatograph is usually coupled directly to the mass spectrometer source. The interface may include a diverter valve for shunting the column effluent and isolating the mass spectrometer source. All components of the interface should be glass or glass-lined stainless / i Method T09 227 steel. The interface components should be compatible with 300°C temperatures. Cold spots and/or active surfaces (adsorption sites) in the GC/MS interface can cause peak tailing and peak broadening. It is recommended that the GC column be fitted directly into the MS source. Graphic ferrules should be avoided in the GC injection area since they may adsorb TCDD. Vespel• or equivalent ferrules are recommended. 7 .4.3 Mass Spectrometer. The static resolution of the instru-ment must be maintained at a minimum of 10,000 (10 percent valley). The mass spectrometer must be operated in a selected ion monitoring (SIM) mode with a total cycle time (including voltage reset time) of one second or less (Section 12.3.4.1). At a minimum, ions that occur at the following masses must be monitored: 2,31718-TCDD 1 .2 ,3 ,4, 7 ,8-HiCDD DCDD 258.9300 326 .8521 394. 7742 319.8965 389.8156 457 .7377 321.8936 391.8127 459.7347 331.9368 333.93338 7.4.4 Data System. A dedicated computer data system is employed to control the rapid multiple ion monitoring process and to acquire the data. Quantification data (peak areas or peak heights) and SIM traces (displays of intensities of each m/z being monitored as a function of time) must be acquired during the analyses. Quantifications may be reported based upon computer-generated peak areas or upon measured peak heights (chart recording). The detector zero setting must al low peak-to-peak measurement of the noise on the baseline.
228 Methods for Determination of Toxic Organic Compounds in Air 7.4.5 GC Column. A fused silica column (30 m x 0.25 mm 1.0.) coated with DB-5, 0.25 u film thickness (J & S Scientific, Inc., Crystal Lake, IL) is utilized to separate each of the several tetra-through octa-PCDDs, as a group, from all of the other groups. This column also resolves 2,3,7,8-TCDD from all 21 other TCDD isomers; therefore, 2,3,7,8-TCDD can be detennined quantitatively if proper calibration procedures are followed as per Sections 12.3 through 12.6. Other columns may be used for detennination of PCDDs, but separation of the wrong PCDD isomers must be demonstrated and documented. Minimum acceptance criteria must be determined as per Section 12.1. At the beginning of each 12-hour period (after mass resolution has been demonstrated) during which sample extracts or concentration calibration solutions will be analyzed, column operating conditions must be attained for the required separation on the column to be used for samples. 7.5 All required syringes, gases, and other pertinent supplies to operate the HRGC/HRMS system. 7.6 Airtight, labeled screw-capped containers to hold the sample car-tridges (perferably glass with Teflon seals or other noncontaminat-ing seals). 7.7 Data sheets for each sample for recording the location and sample time, duration of sample, starting time, and volume of air sampled. 7.8 Balance capable of weighing accurately to _!_0.001 g. 7.9 Pipettes, micropipets, syringes, burets, etc., to make calibra-tion and spiking solutions, dilute samples if necessary, etc., including syringes for accurately measuring volumes such as 25 ul and 100 ul of isotopically labeled dioxin solutions. 7.10 Soxhlet extractors capable of extracting GMW PS-I PUF adsqrbent cartridges (2.3" x 5" length), 500-ml flask, and condenser. Method T09 229 7.11 Vacuum drying oven system capable of maintaining the PUF car-tridges being evacuated at 240 torr (flushed with nitrogen) overnight. 7.12 Ice chest -to store samples at 0°C after collection. 7.13 Glove box for working with extremely toxic standards and reagents with explosion-proof hood for venting fumes from solvents reagents, etc. 7.14 Adsorbtion columns for column chromatography - I cm x 10 cm and I cm x 30 cm, with stands. 7.15 Concentrator tubes and a nitrogen evaporation apparatus with variable flow rate. 7.16 Laboratory refrigerator with chambers operating at 0°C and 4°C. 7.17 Kuderna-Danish apparatus -500 ml evaporating flask, 10 ml graduated concentrator tubes with ground-glass stoppers, and 3-ball macro Snyder Column (Kontes K-570001-0500, K-50300-0121, and K-56gQQl-219, or equivalent). 7.18 Two-ball micro Snyder Column, Kuderna-Danish (Kontes 569001-0219, or equivalent). 7.19 7.20 Stainless steel spatulas ar.d spoons. Minivials - l ml, borosilicate glass, with conical reservoir and screw caps lined with Teflon-faced silicone disks, and a vial holder. 7.21 Chromatographic columns for Carbopak cleanup -disposable 5-ml graduated glass pipets, 6 to 7 mm ID. 7.22 Desiccator. 7.23 Polyester gloves for handling PUF cartridges and filter. 7.24 Die -to cut PUF plugs. 7.25 Water bath equipped with concentric ring cover and capable of being temperature-controlled within ~z•c. 7.26 Erlenmeyer flask, 50 ml. 7.27 Glass vial, 40 ml. 7.28 Cover glass petri dishes for shipping filters. 7.29 Fritted glass extraction thimbles. 7.30 Pyrex glass tube furnace system for activating silica gel at 180°C under purified nitrogen gas purge for an hour, with capability of raisir.g temperature gradually.
230 Methods for Determination of Toxic Organic Compounds in Air [NOTE: Reuse of glassware should be minimized to avoid the risk of cross-contamination. All glassware that is used, especially glassware that is reused, must be scrupulously cleaned as soon as possible after use. Rinse glassware with the last solvent used in it and then with high-purity acetone and hexane. Wash with hot water containing detergent. Rinse with copious amount of tap water and several portions of distilled water. Drain, dry, and heat in a muffle furnace at 400°C for 2 to 4 hours.· Volumetric glassware must not be heated in a muffle furnace; rather, it should be rinsed with high-purity acetone and hexane. After the glassware is dry and cool, rinse it with hexane, and store it inverted or capped with solvent-rinsed aluminum foil in a clean environment.] 8. Reagents and Materials 8.1 Ultrapure glass wool, silanized, extracted with methylene chloride and hexane, and dried. 8.2 Ultrapure acid-washed quartz fiber filters for PS-I Sampler (Pallfex 2500 glass, or equivalent). 8.3 Benzene (Burdick and Jackson, glass-distilled, or equivalent). 8.4 Hexane (Burdick and Jackson, glass-distilled, or equivalent). 8.5 Alumina, acidic -extracted in a Soxhlet apparatus with methylene chloride for 6 hours (minimum of 3 cycles per hour) and activated by heating in a foil-covered glass container for 24 hours at 190°C. 8.6 Silica gel -high-purity grade, type 60, 70-230 mesh; extracted in a Soxhlet apparatus with methylene chloride for 6 hours (minimum of 3 c1cles per hour) and activated by heating in a foil-covered glass container for 24 hours at 130°C. 8.7 Silica gel impregnated with 40 percent (by weight) sulfuric acid -prepared by adding two parts (by weight) concentrated sulfuric acid to three parts (by weight) silica gel (extracted and activated) and mixiing with a glass rod until free of lumps; stored in a screw-capped glass bottle. Method T09 231 8.8 Graphitized carbon black (Carbopak C or equivalent), surface of approximately 12 m2/g, 80/100 mesh -prepared by thoroughly mixing 3.6 grams Carbopak C and 16.4 grams Cel1te 545• in a 40-ml vial and activating at 130°C for six hours; stored in a desiccator. 8.9 Sulfuric Acid, ultrapure, ACS grade, specific gravity 1.84. 8.10 Sodium Hydroxide, ultrapure, ACS grade. 8.11 Native and isotopically labeled PCDO/PCDF isomers for calibration and spiking standards, from Cambridge Isotopes, Cambridge, MA. 8.12 n-decane (Aldrich Gold Label grade [090-1), or equivalent). 8.13 Toluene (high purity, glass-distilled). 8.14 Acetone (high purity, glass-distilled). 8.15 Filters, quartz fiber -Pall flex 2500 QAST, or equivalent. 8.16 Ultrapure nitrogen gas (Scott chromatographic grade, or equivalent). 8.17 Methanol (chromatographic grade). 8.18 Methylene chloride (chromatographic grade, glass-distilled). 8.19 Dichloromethane/hexane (3:97, v/v), chromatographic grade. 8.20 Hexane/dichloromethane (l:l, v/v), chromatogtraphic grade. 8.21 Perfluorokerosene (PFK), chromatographic grade. 8.22 Celite 545•, reagent grade, or equivalent. 8.23 Membrane filters or filter paper with pore sizes less than 25 um, hexane-rinsed. 8.24 Granular anhydrous sodium sulfate, reagent grade. 8.25 Potassium carbonate-anhydrous, granular, reagent grade. 8.26 Cyclohexane, glass-distil led. 8.27 Tridecane, glass-distilled. 8.28 2,2,3-trimethylpentane, glass-distil led. 8.29 Isooctane, glass-distilled. 8.30 Sodium sulfate, ultrapure, ACS grade. 8.31 Polyurethane foam -3 inches thick sheet stock, polyether type used in furniture upholstering, density 0.022 g/cm3.
232 Methods for Determination of Toxic Organic Compounds in Air 8.32 Concentration calibration solutions (Table 1) -four tridecane solutions containing 13c12-l ,2,3,4-TCDD (recovery standard) and unlabeled 2,3,7,8-TCDD at varying concentrations, and 13c12-2,3,7,8-TCDD (internal standard, CAS RN 80494-19-5). These solutions must be obtained from the Quality Assurance Division, U.S. EPA, Environmental Monitoring Systems Laboratory (EMSL-LV), Las Vegas, Nevada, and must be used to calibrate the instrument. However, secondary standards may be obtained from commercial sources, and solutions may be prepared in the analytical laboratory. Traceability of standards must be verified against EPA-supplied standard solutions by procedures documented in laboratory SOPs. Care must be taken to use the correct standard. Serious overloading of instruments may occur if concentration calibration solutions intended for low-resolution MS are injected into the high-resolution MS. 8.33 Column performance check mixture dissolved in I ml of tridecane from Quality Assurance Division (EMSL-LV). Each ampule of this solution will contain approximately JO ng of the following ccrnponents (A) eluting near 2,3,7,8-TCDD and of the first (F) and last-eluting (L) TCDDs, when using the recooimended columns at a concentration of JO pg/ul of each of these isomers: o unlabeled 2,3,7,8-TCDD 13 o c12-2,3,7 ,8-TCDD o 1,2,3,4-TCDD (A) o 1,4,7,8-TCDD (A) o 1,2,3,7-TCDD (A) o 1,2,3,8-TCDD (A) o 1,3,6,8-TCDD (F) o 1,2,8,9-TCDD (L) If these solutions are unavailable from EPA, they should be prepared by the analytical laboratory or a chemical supplier and analyzed in a manner traceable to the EPA performance check mixture designed for 2,3,7,8-TCDD monitoring. Similar mixtures of isotopically labeled compounds should be prepared to check performance for monitoring other specific forms of TCDD that are of interest. ;,, }· 1 l 4 1 t ;t -l , i ;i \l' t I t t if ' l 1 I 1 -1 I 9. Method T09 233 8.34 Sample fortification solution -isooctane solution contain-ing the internal standard at a nominal concentration of JO pg/ul. 8.35 Recovery standard spiking solution -tridecane solution con-taining the isotopically labeled standard (13c12-2,3,7,8-TCDD and other PCDDs of interest) at a concentration of 10.0 pg/ul. 8.36 Field blank fortification solutions -isooctane solutions containing the following: • Solution A: 0 Solution 8: 10.0 pg/ul of unlabeled 2,3,7,8-TCDD 10.0 pg/ul of unlabeled 1,2,3,4-TCDD (NOTE: These reagents and the detailed analytical procedures described herein are designed for monitoring TCDD isomer concentrations of 6.0 pg/m3 to 37 pg/m3 each, If ambient concentrations should exceed these levels, concentrations of calibrations and spiking solutions will need to be modified, along with the detailed sample preparation procedures. The reagents and procedures described herein are based on Appendix 8 of the Protocol for the Analysis of 2,3,7,8-TCDD (Section 2.2.2) ccrnbined with the evaluation of the high volume air sampler for PCDD. Preparation of PUF Sampling Cartridge 9.1 The PUF adsorbent is a polyether-type polyurethane foam (density No. 3014 or 0.0225 g/cm3) used for f~rniture upholstery. 9.2 The PUF inserts are 6.0-cm diameter cylindrical plugs cut from 3-inch sheet stock and should fit, with slight compression, in the glass cartridge, supported by the wire screen (Figure 1). During cutting, the die is rotated at high speed (e.g., in a drill press) and continuously lubricated with water. 9.3 For initial cleanup, the PUF plug is placed in a Soxhlet appara-tus and extracted with acetone for 14-24 hours at approximately 4 cycles per hour. When cartridges are reused, 5% diethyl ether inn-hexane can be used as the cleanup solvent. 9.4 The extracted PUF is placed in a vacuum oven connected to a water aspirator and dried at rocrn temperature for approximately 2-4 hours (until no solvent odor is detected).
234 Methods for Determination of Toxic Organic Compounds in Air 9.5 The PUF is placed into the glass sampling cartridge using poly-ester gloves. The module is wrapped with hexane-rinsed aluminum foii, placed in a labeled container, and tightly sealed. 9.6 At least one assembled cartridge from each batch must be analyzed, as a laboratory blank, using the procedures described in Section 11, before the batch is considered acceptable for field use. A blank level of <10 ng/plug for single compounds is considered to be acceptable. 10. Sample Collection 10.1 Description of Sampling Apparatus 10.1.1 The entire sampling system is diagrammed in Figure 2. A unit specifically designed for this method is commercially available (Model PS-1 -General Metal Works, Inc., Village of Cleves, Ohio). 10.1.2 The sampling module (Figure 1) consists of a glass sampl-ing cartridge and an air-tight metal cartridge holder. The PUF is retained in the glass sampling cartri~ge. 10.2 Calibration of Sampling System 10.2.1 The airflow through the sampling system is monitored by a Venturi/Magnehelic assembly, as shown in Figure 2. Assembly must be audited every six months using an audit calibration orifice, as described in the U.S. EPA High Volume Sampling Method, 40 CFR SO, Appendix B. A single-point calibration must be perfonned before and after each sample collection, using the procedure described in Section 10.2.2. 10.2.2 Prior to calibration, a "durrrny" PUF cartridge and filter are placed in.the sampling head and the sampling motor is activated. The flow control valve is fully opened and the voltage variator is adjusted so that a sample flow rate corresponding to llOi of the desired flow rate is indicated on the Magnehelic (based on the previously obtained multipoint calibration curve), The motor is allowed to wann up for 10 minutes and then the flow control . . Method T09 235 valve is adjusted to achieve the desired flow rate. The ambient temperature and barometric pressure should be recorded on an appropriate data sheet. 10.2.3 The calibration orifice is placed on the sampling head and a manometer is attached to the tap on the calibration orifice. The sampler is momentarily turned off to set the zero level of the manometer. The sampler is then switched on and the manometer reading is recorded after a stable reading 1s achieved. The sampler is then shut off. 10.2.4 The calibration curve for the orifice is used to cal-culate sample flow from the data obtained in Section 10.2.3, and the calibration curve for the Venturi/ Magnehelic assembly is used to calculate sample flow from the data obtained in Section 10.2.2. The calibra-tion data should be recorded on an appropriate data sheet. If the two values do not agree within 101, the sampler should be inspected for damage, flow blockage, etc. If no obvious problems are found, the sampler should be recalibrated (multipoint) according to the U.S. EPA High Volume Sampling Method (Section 10.2.1). 10.2.5 A multipoint calibration of the calibration orifice, against a primary standard, should be obtained annually. 10.3 Sample Collection 10.3.1 After the sampling system has been assembled and calibrated as described in Sections 10.1 and 10.2, it can be usea t0 coll~ct air samples, as described in Section 10.3.2 . 10.3.2. The samples should be located in an unobstructed area, at least two meters from any obstacle to air flow. The exhaust hose should be stretched out in the down-wina direction to prevent recycling of air.
236 Methods for Determination of Toxic Organic Compounds in Air 10.3.3 A clean PUF sampling cartridge and quartz filter are removed from sealed transport containers and placed in the sampling head using forceps and gloved hands. The head ls tightly sealed into the sampling system. The aluminum foil wrapping is placed back in the senled container for later use. 10.3.4 The zero reading of the Magnehelic is checked. Ambient 10.3.5 temperature, barometric pressure, elapsed time meter setting, saw.pler serial number, filter number, and PUF cartridge number are recorded on a suitable data sheet, as illustrated in Figure 3. The voltage variator and flow control valve are placed at the settings used in Section 10.2.3, and the power switch is turned on. The elapsed time meter is 3Cti-vated and the start time is recorded. The flow (Magne-helic setting) is adjusted, if necessary, using tne flow control valve. 10.3.6 The Magnehelic reading is recorded ever_y six hou,s during the sampling period. The calibration curve (Section 10.2.4) is used to calculate the flow rate. Ambient temperature and barometric pressure are recorded at the beginning and end of the sampling period. 10.3.7 At the end of the desired sampling period, the power is turned off and the filter and PUF r.artridges are wrapp~d with the original aluminum foil and placed in sealed, labeled containers for transport back to the labor~tory. 10.3.8 The Magnehelic calibration is checked using the cal;-bration orifice, as described in Section 10.2.4. If calibration deviates by more than 10% from the initial reading, the flow data for that sample must be marked as suspect and the sampler should be inspected and/or removed from service. ,,_ !· :, ::;: ·, ·i ;'r ,, { h. r; f i t ' ~I ' ]! ., Method T09 237 10.3.9 At least one field filter/PUF blank will be returned to the laboratory with each group of samples. A field blank is treated exactly as a sample except that no air is drawn through the filter/PUF cartridge assemblJ. 10.3.10 Samples are stored at 20°C in an ice chest until receipt at the analytical laboratory, after which they are refrigerated at 4°C. 11. Sample Extraction 11.1 Immediately before use, charge the Soxhlet apparatus with 200 to 250 ml of benzene and reflux for 2 hours. Let the apparatus cool, disassemble it, transfer the benzene to a clean glass container, and retain it as a blank for later analysis, if required. After sampling, spike the cartridges and filters with an internal standard (Table 1). After spiking, place the PUF cartridge and filter together 1n the Soxhlet apparatus (the use of an extraction thimble is optional). (The filter and PUF cartridge are analyzed together in order to reach detection limits, avoid questionable interpretation of the data, and mini-mize cost.) Add 200 to 250 ml of benzene to the apparatus and relux for 18 hours at a rate of at least 3 cycles per hour. 11.2 Transfer the extract to a Kuderna-Danish (K-0) apparatus, concen-trate it to 2 to 3 ml, and let it cool. Rinse the column and flask with 5 ml of benzene, collecting the rinsate in the concen-trator tube to 2 to 3 ml. Repeat the rinsing and concentration steps twice more. Remove the concentrator tube from the K-0 apparatus and carefully reduce the extract volume to approximately 1 ml with a stream ot nitrogen using a flow rate and distance above the solution such that 3 gentle rippling of the solution surface is observed.
238 Methods for Determination of Toxic Organic Compounds in Air l 1.3 Perfonn the following column chromatographic procedures for sample extraction cleanup. These procedures have been demonstrated to be effective for a mixture consisting of: 0 1,2,3,4-TCDD 0 1 ,2 ,3 ,4, 7 ,8-HxCDD 0 OCDD 0 2,3,7,8-TCDD 11.3.1 Prepare an acidic silica gel column as follows (Figure 4): Pack a 1 cm x 10 cm chromatographic column with a glass wool plug, a 1-cm layer of NazS04/KzC03 (1:1), 1.0 g of silica gel (Section 8.6), and 4.0 g of 40-percent (w/w) sulfuric acid-impregnated silica gel (Section 8.7). Pack a second chromatographic column (1 cm x 30 cm) with a glass wool plug and 6.0 g of acidic alumina (Section 8.5), and top it with a 1-cm layer of sodium sulfate (Section 8.30). Add hexane to the columns until they are free of channels and air bubbles. 11.3.2 Quantitatively transfer the benzene extract (1 ml) from the concentrator tub to the top of the silica gel column. Rinse the concentrator tube with 0.5-ml portions of hexane. Transfer the rinses to the top of the silica gel column. 11.3.3 Elute the extract from the silica gel column with 90 of ml hexane directly into a Kudena-Danish concentrator tube. Concentrate the eluate to 0.5 ml, using nitro-gen blowdown, as necessary. 11.3.4 Transfer the concentrate (0.5 ml) to the top of the alumina column. Rinse the K-D assembly with two 0.5-ml portions of hexane, and transfer the rinses to the top of the alumina column. Elute the alumina column with 18 ml hexane until the hexane level is just below the top of the sodium sulfate. Discard the eluate. Do not let the columns reach dryness (i.e., maintain a solvent "head"). ,f l: f Method T09 239 11.3.5 Place 30 ml of 201. (v/v) methylene chloride in hexane on top of the alumina column. and elute the TCDDs from the column. Collect this fraction in a 50-ml Erlenmeyer fl ask. 11.3.6 Certain extracts, even after cleanup by column chroma-tography, contain interferences that preclude detennination of TCDD at low parts-per-trillion levels. Therefore, a cleanup step is included using activated carbon which selectively retains planar molecules such as TCDDs. The TCDDs are then removed from the carbon by elution with toluene. Proceed as follows: Prepare an 181 Carbopak C/Celite 545• mixture by thoroughly mixing 3.6 grams Carbopak C (80/100 mesh) and 16.4 grams Ce lite 545• in a 40-ml vial. Activate the mixture at 130°C for 6 hours, and store it in a desiccator. Cut off a clean 5-ml disposable glass pipet at the 4-ml mark. Insert a plug of glass wool (Section 8.1) and push it to the 2-ml mark. Add 340 mg of the activated Carbopak/Celite mixture followed by another glass wool plug, Using two glass rods, push both glass wool plugs simultaneously toward the Carbopak/Celite plug to a length of 2.0 to 2.5 cm. Pre-elute the column with 2 ml of toluene followed by 1 ml of 75:20:5 methylene chloride/methanol/ benzene, 1 ml of 1:1 cyclohexane in methylene choride, and 2 ml of hexane. The flow rate should be less than 0.5 ml per minute. While the column is still wet with hexane, add the entire elute (30 ml) from the alumina column (Section 11.3.5) to the top of the column. Rinse the Erlenmeyer flask that contained the extract twice with 1 ml of hexane and add the rinsates to the top of the column. Elute the column sequentially with two !-ml aliquots of hexane, 1 ml of 1:1 cyclohex-ane in methylene chloride, and 1 ml of 75:20:5 methylene
240 Methods for Determination of Toxic Organic Compounds in Air 12. chloride/mentanol/benzene, Turn the column upside down and elute the TCDD fraction into a concentrator tube with 6 ml of toluene. Wann the tube to approxi-mately 60°C and reduce the toluene volume to approxi-mately I ml using a stream of nitrogen. Carefully transfer the residue into a !-ml minivial and, again at elevated temperature, reduce the volume to about 100 ul using a stream of nitrogen. Rinse the concen-trator tube with 3 washings using 200 ul of 1% toluene in CH2Cl2 each time. Add 50 ul of tridecane and store the sample in a refrigerator until GC/MS analysis is performed. HRGC/HRMS System Perfonnance Criteria The laboratory must document that the system performance criteria specified in Sections 12.1, 12.2, and 12.3 have been met before analysis of samples. 12.1 GC Column Perfonnance 12. I. I Inject 2 ul of the column performance check solution (Section 8.33) and acquire selected ion monitoring (SIM) data for m/z 258.930, 319.897, 321.894, and 333.933 within a total cycle time of ~l second. 12.1.2 The chromatographic peak separation between 2,3,7,8-TCDD and the peaks representing any other TCDD isomers must be resolved with a valley of ~25:, where Valley Percent = (x/y) ( JOO) x = measured distance from extroplated baseline to minimum of valley; and y = the peak height of 2,3,7 ,8-TCDD. [Note: It is the responsibility of the laboratory to verify the conditions suitable for the appropriate resolution of 2 ,3, 7 ,8-TCDD fr001 a 11 other TCDD isomers. The column performance check solution also contains the TCDD isomers eluting first and last under the analytical conditions specified in this protocol, thus defining Method T09 241 the retention time window for total TCDD determination. The peaks representing 2,3,7,8-TCDD, and the first and last eluting TCDD isomers must be labeled and identified.) 12.2 Mass Spectometer Performance 12.2.1 The mass spectraneter must be operated in the electron (impact) ionization mode. Static mass resolution of at least 10,000 (10% valley) must be demonstrated before any analysis of a set of samples is performed (Section 12.2.2). Static resolution checks must be performed at the beginn-ing and at the end of each 12-hour period of operation. However, it is recommended that a visual check (e.g., not documented) of the static resolution be made using the peak matching unit before and after each analysis. 12.2.2 Chromatography time for TCDD may exceed the long-term mass stability of the mass spectraneter; therefore, mass drift correction is mandatory. A reference compound (high boiling perfluorokerosene [PFK] is recommended) is introduced into the mass spectrometer. An acceptable lock mass ion at any mass between m/z 250 and m/z 334 (m/z 318.979 from PFK is recanmended) must be used to monitor and correct mass drifts. [NOTE: Excessive PFK may cause background noise problems and contamination of the source, resulting in an increase in "downtime" for source cleaning. Using a PFK molecular leak, tune the instrument to meet the minimum required mass resolution of 10,000 (JO: valley) at m/z 254.986 (or any other mass reasonably close to m/z 259). Cali-brate the voltage sweep at least across the mass range m/z 259 to m/z 344 and verify that m/z 330.979 from PFK (or any other mass close to m/z 334) is measured within !5 ppm (i.e., 1.7 mmu). Document the mass resolution by recording the peak profile of the PFK reference peak m/z 318.979 (or any other reference peak at a mass close to m/z 320/322). The format of the peak profile represen-tation must allow manual determination of the resolution;
242 Methods for Determination of Toxic Organic Compounds in Air i.e., the horizontal axis must be a calibrated mass scale (mmu or ppm per division). The result of the peak width measurement (perfonned at 5 percent of the maximum) must appear on the hard copy and cannot exceed 31.9 nrnu or 100 ppm.] 12.3 Initial Calibration Intitial calibratior. is required before any samples are analyzed for 2,3,7,8-TCDD. Initial calibration is also required if any routine calibration does not meet the required criteria listed in Section 12.6. 12.3.1 All concentration calibration solutions listed in Table 1 must be utilized for the initial calibration. 12.3.2 Tune the instrument with PFK as described in Section 12.2.2. 12.3.3 Inject 2 ul of the column performance check solution (Sect ion 8.33) and acquire SIM mass spectral data for m/z 258.930, 319.897, 321.894, 331.937, and 333.934 within a total cycle tfme of ~l second. The laboratory must not perform any further analysis until it has been demon-strated and documented that the criterion listed in Section 12.1.2 has been met. 12.3.4 Using the same GC (Section 12.1) and MS (Section 12.2) conditions that produced acceptable results with the column performance check solution, analyze a 2-ul aliquot of each of the 5 concentration calibration solutions in triplicate with the gas chromatographic operating parameters shown in Table 2. 12.3.4.l Total cycle time for data acquisition must be ~l second. Total cycle time includes the sum of all the dwel 1 times and voltage reset times. ,: , l} 'i \:. :~ r-f . .,.. . .. 1,~ Method T09 243 12.3.4.2 Acquire SIM data for the following selected characteristic ions: m/z 258.930 319.897 321.894 331.937 333.934 Com.e_ound TCDD -COCl un 1 abe 1 ed TCDD un 1 abe 1 ed TCDD 13c12-2,3,7,8-TCDD, 13c12-l,2,3,4-TCDD 13c12-2,3,7,8-TCDD, 13c12-l,2,3,4-TCDD 12.3.4.3 The ratio of intergrated ion current for m/z 319.897 to m/z 321.894 for 2,3,7,8-TCDD must be between 0.67 and 0.87 (_:131). 12.3.4.4 The ratio of integrated ion current for m/z 331.937 to m/z 333.934 for 13c12-2,3,7,8-TCDD and 13c12-1,2,3,4-TCDD must be between 0.67 and 0.87. 12.3.4.5 Calculate the relative response factor for unlabeled 2,3,7,8-TCDD [RRF(I)] relative to 13c12-2,3,7,8-TCDD and for labeled 13c12 2,3,7,8-TCDD [RRF(II)] relative to 13c12 1 ,2,3,4-TCDD as follows: RRF(J) • __ _ Ax • 01s -Ox • AIS RRF(II)• __ _ AIS • ORS --01s • ARS
244 Methods for Determination of Toxic Organic Compounds in Air where: Ax A1s ARS 01s • ORS• Ox sum of the integrated abundances of m/z 319.897 and m/z 321.894 for unlabeled 2,3,7,8,-TCDD. sum of the integrated abundances of m/z 331.937 and m/z 333.934 for 13c12-2,3,7,8-TCDD. sum of the integrated abundances for m/z 331.937 and m/z 333.934 for 13c12-l,2,3,4-TCDD. quantity (pg) of 13c12~2,3,7,8-TCDD injected. quantity (pg) of 13c12-l,2,3,4-TCDD injected. quantity (pg) of unlabeled 2,3,7,8-TCDD injected. 12.4 Criteria for Acceptable Calibration The criteria listed below for acceptable calibration must be met before analysis of any sample is performed. 12.4.1 The percent relative standard deviation (RSD) for the response factors from each of the triplicate analyses for both unlabeled and 13c12-2,3,7,8-TCDD must be less than +201. 12.4.2 The variation of the five mean RRFs for unlabeled 2,3,7 ,8-TCDD obtained from the triplicate analyses must be less than +20'.t RSD. 12.4.3 SIM traces for l3c12-2,3,7 ,8-TCDD must present a signal-to-noise ratio ~10 for 333.934. 12.4.4 Isotopic ratios (Sections 12.3.4.3 and 12.3.4.4) must be within the allowed range. [NOTE: If the criteria for acceptable calibration listed in Sections 12.4;1 and 12.4.2 have been met, the RRF can be considered independent of the analyte quantity for the calibration concentration range. The mean RRF froo, five triplicate determinations for unlabeled 2,3,7 ,8-TCDD and for 13c122,3,7,8-TCDD will be used for all calculations until routine calibration criteria (Section 12.6) are no longer met. At such time, new mean RRFs will be calculated from a new set of five triplicate determinations.) r '• 1~ r ·-f' r '.!:~ ,. ·l"I f f' -~'l.i ~1-l,': Method T09 245 12.5 Routine Calibration Routine calibration must be performed at the beginning of each 12-hour period after successful mass resolution and GC column performance check runs. 12.5.1 Inject 2 ul of the concentration calibration solution (Section 8.32) that contains 5.0 pg/ul of unlabeled 2,3,7 ,8-TCDD, 10.0 pg/ul of 13c12-2,3,7,8-TCDD, and 5.0 pg/ul 13c12-l,2,3,4-TCDD. Using the same GC/MS/DS conditions as in Sections 12.1, 12.2, and 12.3, deter-mine and document acceptable calibration as provided in Section 12 .6. 12.6 Criteria for Acceptable Routine Calibration The following criteria must be met before further analysis is performed. If these criteria are not met, corrective action must be taken and the instrument must be recalibrated. 12.6.1 The measured RRF for unlabeled 2,3,7,8-TCDD must be within !20 percent of the mean values established (Section 12.3.4.5) by triplicate analyses of concen-tration calibration solutions. 12.6.2 The measured RRF for 13c1r2,3,7,8-TCDD must be within !20 percent of the mean value established by triplic~te analyses of concentration calibration solutions (Section 12.3.4.5). 12.6.3 Isotopic ratios (Sections 12.3.4.3 and 12.3.4.4) must b~ within the allowed range. 12.6.4 lf one of the above criteria is not satisfied, a second attempt can be made before repeating the entire initial-ization process (Section 12.3). [NOTE: An initial calibration must be carried out whenever any HRCC solution is replaced.) 13. Analytical Procedures 13.1 Remove the sample extract or blank from storage, allow it to warm to ambient laboratory temperature, and add 5 ul of reco\·ery standard solution. With a stream of dry, purified nitrogen, reduce the extract/blank volume to 20 ul.
246 Methods for Determination of Toxic Organic Compounds in Air 13.2 Inject a 2-ul aliquot of the extract into the GC, which should be operating under the conditions previously used (Section 12.1) to produce acceptable results with the performance check solution. 13.3 Acquire SIM data using the same acquisition time and MS operating conditions previously used (Section 12.3.4) to determine the relative response factors for the following selected characteristic ions: m/z 258.930 319.897 321.894 331.937 333.934 Com.e_ound TCDD -COCl (weak at detection limit level) un 1 abe led TCDD un l abe 1 ea TCDD 13 c12-2,3,7,8-TCDD, 13c12-2,3,7 ,8-TCDD, 13 c12-l,2,3,4-TCDD, 13c 12-1 ,2 ,3 ,4-TCDD, 13.4 Identification Criteria 13.4.1 The retention time (RT) (at maximum peak height) of the sample component m/z 319.897 must be within -1 to +3 seconds of the retention time of the peak for the isotopically labeled internal standard at m/z 331.937 to attain a positive identification of 2,3,7,8-TCDD. Retention times of other tentatively identified TCDDs must fall within the RT window established by analyzing the column performance check solution (Section 12.1). Retention times are required for all chromatograms. 13.4.2 The ion current responses for m/z 258.930, 319.897 and 321.894 must reach their maxima simultaneously (:_l scan), and al 1 ion current intensities must be ~2.5 times noise level for positive ide~tification of a TCDD. 13.4.3 The integrated ion current at m/z 319.897 must be between 67 and 87 percent of the ion current response at m/z 321.894. '}, Method T09 247 13.4.4 The integrated ion current at m/z 331.937 must be between 67 and 87 percent of the ion current response at m/z 333.934. 13;4.5 The integrated ion currents for m/z 331.937 and 333.934 must reach their maxima within _:l scan. 13.4.6 The recovery of the internal standard 13c12-2,3,7,8-TCDD must be between 40 and 120 percent. 14. Calculations 14.1 Calculate the concentration of 2,3,7,8-TC0D (or any other TC00 isomer) using the formula: where: Cx Cx 2 Ax • 01s AIS • V • RRF(I) quantity (pg) of unlabeled 2,3,7,8-TCDD (or any other unlabeled TCDD isomer) present. Ax s sum of the integrated ion abundances determined for m/z 319.897 and 321.894. A1s = sum of the integrated ion abundances determined for m/z 331.937 and 333.934 of 13c12-2,3,7,8-TCDD (IS■ internal standard). 01s = quantity (pg) of 13c12-2,3,7,8-TC00 added to the sample before extraction (0is ■ 500 pg). V = volume (m3) of air sampled. RRF(I) Calculated mean relative response factor for unlabeled 2,3,7 ,8-TCDD relative to 13c12-2,3,7,8-TCDD. This value represents the grand mean of the RRF(I)s obtained in Section 12.3.4.5.
248 Methods for Determination of Toxic Organic Compounds in Air 14.2 Calculate the recovery of the internal standard l3c12-2,3,7,8-TCDD, measured in the sample extract, using the formula: where: Internal standard, percent recovery= A IS . ORS x 1D0 ARS • RRF(JI) · o15 A15 and 015 ARs same definitions as above (Section 14.1) sum of the integrated ion abundances determined for m/z 331.937 and 333.934 of 13c12-! ,2 ,3 ,4-TCDD (RS = recovery ORS RRF (II) standard). quantity (pg) of 13c12-!,2,3,4-TCDD added to the sample residue before HRGC-HRMS analysis (DRS= 500 pg). Calculated mean relative response factor for labeled 13c12-2,3,7 ,8-TCDD. This value represents the grand mean of the RRF( JJ)s calculated in Section 12.3.4.5. 14.3 Total TCDD Concentration 14.3.1 All positively identified isomers of TCDD must be within the RT window and meet all identification criteria listed in Sections 13.4.2, 13.4.3, and 13.4.4. Use the expression in Section 14.1 to calculate the concentrations of the other TCDD isomers, with Cx be-coming the concentration of any unlabeled TCDD isomer. 14.4 Estimated Detection Limit I 4 .4 .1 For samples in which no unlabeled 2,3,7 ,8-TCDD was detected, calculate the estimated minimum detectable concentration. The background area is determined by integrating the ion abundances for m/z 319.897 and 321.894 in the appropriate region and relating that height area to an estimated concentration that would produce that product area. Use the formula: CE (2.5) • (Ax) ' (015) (A15) • RRF(I) · (W) where: 14.5 Method T09 249 CE • estimated concentration of unlabeled 2,3,7,8-TCDD required to produce Ax, Ax • sum of integrated ion abundance for m/z 319.897 and 321.894 in the same group of ~25 scans used to measure A15, A1s • sum of integrated ion abundance for the appropriate ion characteristic of the internal standard, m/z 331.937 and m/z 333.934. 015, RRF(I), and V retain the definitions previously stated in Section 14.1. Alternatively, if peak height measurements are used for quantification, measure the estimated detection limit by the peak height of the noise in the TCDD RT window. The relative percent difference (RPD) is calculated as follows: S1 -S2 RPD • I I 'Mean Concentration\ 1 s1 -s2 I ht+ -Tzm X 100 S1 and S2 represent sample and duplicate sample results. 14.6 The total sample volume (Vml is calculated from the periodic flow readings (Magnehelic) taken in Section 10.3,6 using the following equation: Vm• 01 + 02 • • • ON T X -umo where: Vm = total sample volume (m3). 01 02 ···ON= flow rates determined at the beginning, end, mediate points during sampling (L/minute). N T number of data points averaged. = elapsed sampling time (minutes). and inter-
250 Methods for Determination of Toxic Organic Compounds in Air 14.7 The concentration of compound in the sample is calculated using the following equation: where: Vs , Vm X __!;. X 760 298 273 + tA Vs• total sample volume (m3) at 25°C and 760 mm Hg pressure. Vm • total sample flow (m3) under ambient conditions. PA• ambient pressure (mm Hg). tA • ambient temperature (°C). 14.8 The concentration of compound in the sample is calculated using the following equation: where: Ax VE CA • Vi x Vs CA= concentration (ug/m3) of analyte in the sample. A = calculated amount of material determined by HRGC/HRMS. Vi • volume (ul) of extract injected. V£ • final volume (ml) of extract. Vs• total volume (m3) of air samples corrected to standard conditions. 15. Performance Criteria and Quality Assurance This section summarizes required quality assurance (QA) measures and provides guidance ~oncerning performance criteria that should be achieved within each laboratory. 15.1 Standard Operating Procedures (SOPs) 15.1.1 Users should generate SOPs describing the following activities in their laboratory: 1) assembly, calibra-tion and operation of the sampling system with make and model of equipment used; 2) preparation, purifica-tion, storage, and handling of sampling cartridges and filters; 3) assembly, calibration and operation of the HRGC/HRMS system with make and model of equipment used; 4) al1 aspects of data recording and processing, in-cluding lists of computer hardware and software used. Method T09 251 15.1.2 SOPs should provide specific stepwise instructions and should be readily available to and understood by the laboratory personnel conducting the work. 15.2 Process, Field, and Solvent Blanks 15.2.1 One PUF cartridge and filter from each batch of approximately 20 should be analyzed, without shipment to the field, for the compounds of interest to serve as process blank. 15.2.2 During each sampling episode, at least one PUF cartridge and filter should be shipped to the field and returned, without drawing air through the sampler, to serve as a field blank. 15.2.3 During the analysis of each batch of samples, at least one solvent process blank (all steps conducted but no PUF cartridge or filter included) should be carried through the procedure and analyzed.
252 Methods for Determination of Toxic Organic Compounds in Air TABLE 1 C(}lPOSITION OF CONCENTRATION CALIBRATION SOLUTIONS Recovert Standards Analtte Internal Standard 13c12-l,2,3,4-TCDD 2,3,7,8-TCOO 13c12-2,3,7,8-TCOD HRCCl 2.5 pg/ul 2.5 pg/ul 10.0 pg/ul HRCC2 5 .0 pg/uL 5.0 pg/uL 10.D pg/ul HRCC3 10.0 pg/ul 10.0 pg/uL 10.0 pg/ul HRCC4 20.0 pg/ul 20.0 pg/ul 10.0 pg/ul HRCC5 40.0 pg/uL 40.0 pg/uL 10.0 pg/ul Sample Fortification Solution 5.0 pg/ul of 13c12-2,3,7,8-TCOO Recovert Standard Spiking Solution 100 pg/uL 13clz-l,2,3,4-TCDD Field Blank Fortification Solutions A) 4.0 pg/ul of unlabeled 2,3,7 ,8-TCOD B) 5.0 pg/ul of unlabeled 1,2,3,4-TCDD TABLE 2 RECOMl-l:NDED GC OPERATING CONDITIONS Co 1 umn coat1 ng SP-2330 (SP 2331) Film thickness 0.20 um Column dimensions 60 m x 0.24 mm Helium linear velocity 28-29 cm/sec at 240°C Initial temperature 200°c Initial time 4 min Temperature program 200°c to 250°c at 4°C/min CP-SIL 88 0.22 um 50 m x 0.22 mm 28-29 cm/sec at 240°C 190°c 3 min 19o•c to 240°c at 5°C/min a: w I-ll) z < u J: !:: z ~.~ 0 z < w C, 0 ii: ~ 1-ct Z UW al Cl) a: Cl) 0 < Cl) -' 0 C, < a: a: wU 0 Cl) -' .... 0 a: :I: 0 a: Q. w Q. I-::, -' Cl) it l-a: 0 Q. Q. ::, Cl) z w w a: u Cl) C, z z <( 1-w a: a: w 0 -' 0 :I: a: w .... -' u:: a: w .... w ~ < c .... w w ~ z Cl) 0 < u C, ::; vi Method T09 253 W Ill z a: .... oww um~ -al Cl) :::!::>< Cl) a: C, C, z ii: C, z z ct 1-w a: a: w .... -' u:: 0 ~ w l: c.:, z ::l C. ~ ~ Cl) ~ w a: ::) c.:, LL
...
~
C:
"' "C C: :::,
0 a.
E 0
(.)
.5:: C: "' E'
0
.5::
X 0 ..... .... 0
C: .Q ...,
"' C:
§
w ..., w
Cl ... 0 ....
"' "C 0 ..r::. ..., w ~
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• 256 Methods for Determination of Toxic Organic Compounds in Air ◄ SODIUM SULFATE ~ ACIOIC ALUMINA I -1.0 OI .... OLASI WOOL P'I.UO (a) ALUMINA COLUMN ~~;\:?:Xi( %<~:f~ti.J -C SULFURIC ACID ON SILICA OEL 1-4.0 ti Jt~~};~hj ....... SILICA OEL I -1 .0 OI ◄ SODIUM SULFATE/POTASSIUM CAIIIONATE 11:11 ....... OLAH WOOL P'I.UO lb) SILICA GEL COLUMN FIGURE 4. MUL TILA YE RED EXTRACT CLEANUP COLUMNS " j ,,; , ; ;;1 'i .,. /~1 •') ,, :~ METHOD T010 DETERMINATION OF ORGANOCHLORINE PESTICIDES Ir AMBIENT AIR USING LOW VOLUME POLYURETHANE FOJ (PUF) SAMPLING WITH GAS CHROMATOGRAPHY/ELECTR1 CAPTURE DETECTOR (GC/ECD) 1. Scope Revision 1.0 June, 1988 1.1 This document describes a method for sampling and analysis of variety of organochlorln~ pesticides in ambient air. The proc is based on the adsorption of chBnicals fran ambient air on polyurethane foam (PUF) using a low volume sampler. 1.2 The low volume PUF sampling procedure is applicable to multic, ponent atmospheres containing organochlorine pesticide concenl fran 0.01 to 50 ug/m3 over 4-to 24-hour s&npllng periods. The detection limit wil 1 depend on the nature of the analyte the length ~f the sampling period. 1.3 Specific compounds for which the method has been employed are listed in Table l. The analysis methodology described in thi document is currently employed by laboratories using EPA Meth 608, The sampling methodology has been formulated to meet th needs of pesticide sampling In a111bient air. 2. Applicable Documents 2,1 ASTM Standards Dl356 -Definitions of Terms Related to Atmospheric Sampling and Analysis. Dl605-60 -Standard Recommended Practices for Sampling Atmospheres for Analysis of Gases and Vapors. E260 -Recommended Practice for General Gas Chroma-tography Procedures. E355 -Practice for Gas Chromatography Terms and Relationships. 2.2 EPA Documents
•
February 17, 1995
Memorandum
TO: Jack Butler
FROM:
RE:
David J. Lown
Dioxin produced and released during September 1993 BCD test
Koppers NPL Site
Morrisville, Wake County
\\ECEIVft,
, lolid Waste
FEB 22 1995
This memo is being prepared to respond to your request for a concise description and
documentation of the dioxin that was produced and released during the BCD test at the Koppers
site in September 1993. The following documentation was given to me by Terry Lyons of the
SITE program during a presentation Mr. Lyons made to EPA Region IV personnel on
December 1, 1994.
Seven soil tests were run during the demonstration and about 15 tons of soil were treated.
Testing parameters were varied during the demonstration. Table 1 shows the parameters that
were varied.
The most toxic dioxin is 2,3, 7,8-TCDD. Before-and-after-treatment soil results for dioxin
are shown in Table 2. The amount of 2,3,7,8-TCDD increased in test runs 1 and 2. (For
example, input soils for test run 1 were below detection limits for 2,3, 7,8-TCDD and output soils
averaged about 11 ug/kg.) The levels of2,3,7,8-TCDD for runs 4 through 7 were all below
detection and no conclusions about the creation or destruction of2,3,7,8-TCDD can be made.
Because of the way the data was collected, exactly how much dioxin was released to the
atmosphere during the demonstration is unknown. Mass-balance calculations suggest that a total
of0.3 grams of dioxin was released to the atmosphere during the demonstration (Table 3). How
much ofthis estimate is 2,3,7,8-TCDD, I do not know.
A high-volume filter air monitor device used during the demonstration detected 1.59e-04
ngldscm 2,3,7,8-TCDD and 8.39e-06 2,3,7,8-TCDF. These results are shown in Table 4.
Runs 1 2 3 4 5 6 TA.kl~ {. BCD Test Parameters Solid Reactor Temp °F 800 800 650 650 800 800 Reagent Bicarb (5%) Non-Bicarb Bicarb (5%) Non-Bicarb ? • ? • Retention 30 min 30 min 30 min 30 min 30 min 30 min
!5 ;o I .... (J) I .... ~ .t,. .... V1 (,.J (S) (S) .... ..... ..... .i,.. (S) .t,. ~ h (S) isl 7) (S) (S) I\.) Awytc 2,3,7,8-TCDD Total TCDD 2,3,7,8-TCDF Tout TCDF Total PcCDD TotaJ Pl:CDF Total HxCDD Total HxCDF TotaJ HpCDD T<nl HpCDP OCDD OCDP TABLE. 2 ANALYTICAL RESULTS 1'0R PCDD/F IN SOIL SAM:PL~ (.etg/kg) TEST RUN l JNPUT OITTPUT TRl-CNl-SI..2 TRI-CN1D-SL2 TIU-CNI-Sl3 TRI-CN2-Sl3DUP -TRJ-CN2-SL3 0.38 u 1.5 u· 7.4 20.6 8.7 6..5 J 7.0 U 87.3 298 99.3 2.0 u 1.4 U 0.74 u 0.66 u 1.0 31.<( I 25.9 J 2.6 u 4.7 I 2.3 2.3 u 2.5 U 141 439 169 134 J 123 J 4.3 u 12_2 3.7 96.8 106 225 658 265 648 J 606 5.5 J 27.8 4.6 2,190 J 1,850 J 275 790 J 252 968 J 944 J 11.2 39.7 7.2 11,60 J 13.100 J 646 J 1,980 J 359 2,,590 J 2,440 J 9.5 I 25.2 . ' 4.1 TR l-CN3-Sl..3 J 8.7 J 86.l u 1.2 u u 11.8 u 138 u 2.8 u 221 J 2.2 J 178 1.9 J J 211 J 3.1 u I ►-CT " t. C (;_ (, •-· -, ' ~ ( r. 1--T r l J ·t r,.1 ' . c.,
~ I .... Q') I .... ~ .t:,. .... V1 w .... IS) .... .... .... .t:,. IS) A ~ -J A (S) ~ -0 ~ Analytc 2,3.7,8-TCDD Total TCDD 2,3,7,8-TCDF Total TCDF Tot.alPl:CDD Total PeCDF Total HJ1.:CDD Tot:il HxCDF Toal HpCDD ToulHpCDF OCDD OCDF TABLE 2-(<ontiaed) ANALYTICAL RF.SULTS FOR PCDD!FJN SOD., SAMPLES (J,tglkg) TESTRUN2 INPUT OlTI'PUT TR2-CN1-Sl2 TR2-CNI -SL3 TR2-CNI-SL3DUP TR2-CN2-SL3 L.6 u 2.◄ J 8.0 J 3.9 3.2 u 2.61 383 466 LS u 2.6 u 1.2 u 1.6 25..3 I 26.4 17,2 79.6 4.5 u 419 661 637 13g J 13_7 u 14.7 36.3 ]07 780 J 1,300 J 1,090 561 J 17.7 24.9 49.◄ 1,750 J 951 J 1.,270 J 1,110 833 J 41.l 47.3 66.6 11,200 J 1,250 J l.ti60 J 1,530 2,190 I 22.0 . 25.6 385 TR2-CN3-SL3 J 2.4 J J 307 u l.4 u 42 409 20.9 J 679 27.l J 632 37.0 J 759 17.7 ..,. n :;o .... 0-, -U) t,. C::J w l-:i ·11 ~ ,, ;fl ( ·, 9 ...., T, ··I r-I, 7 --i ]) -, \~ I C
~ I ..... CJ) I ,..... $ A ,..... V1 LJ ..... CS) .... ..... ..... A CS) A ~ A CS) ~ -u CS) ~ Anlyte 2,3,7,&-TffiD Tow TCT>D 2,3,7,8-TCDF Total TCDF Total.PcCDD Tot31 PcCDF T<nl Hx.CDD Total HxCDF Tocal HpCDD Total Hp(DP OCDD OCDF TABLE 2-(continued) ANALYilCAL RESULTS FOR PCDD/F IN SOIL SAMPLES (pg/kg) TEST RUN 3 INPUT OlITPUT-CANCEI.LED TR3-CNI-SU 1.0 u 3.9 u 0.9 u 29.2 J 7.1 u 113 1 102 550 J 1,730 J 1,040 J 8.MiO 1 1,.510 J ~ :3: T• ;o ,-(J, \,LJ I:. r_;, l,J k! ·o 3: cl ;o n fTl :? >-< r; -·\ r ~ --\ I• Ti r ' ,--0
~ I ..... CJ) I ..... ~ A ..... I.fl w ..... CS) ..... ..... ..... A (S) A ':j ...J A (S) ~ --0 § TABLE 2 (continued) ANALYl'ICAL ~ULTS FOR PCDD/F IN SOIL SAMPLES (µ~/kg) TEST RUN 4 lNPUT OITTPUT Analytc BAT1-CN1-SL2 TR4-CN l-SL3 TR4-CN2-SL3 TR4-CN3-SL3 2,3. 7 ,8-TCDD 2.1 u 0.74 u 1.4 u l.6 u Total TCDD 3.4 u 5.1 u 7.6 u 4.9 u 2,3,7,8-TCDF 1.2 u 1.4-u 1,0 u 0.96 U Total TCDF 22.0 J 2.1 u 1.1 u J. 1 u Total PeCDD 7.2 u 8.4 u 8.1 u 4.1 u Tow PeCDF 122 J 3.1 u 1.2 u 1.5 u Tot.al HxCDD 117 15.4 u 4.2 u 11.9 u Tot.al HxCDF 607 J 2.1 u 1.8 u 2.4 u ToraJ HpCDD 2,000 J 23.1 u 12.2 u 13.9 u Total HpCDF 1,070 J 3.4 u 1.5 u J.4 u OCDD 15,000 J 42.4 u 19.0 u 22.7 u OCDF 3,390 J 2.5 u 1.9 u LO tJ 1 ... t1 '1 1 "' C. r. ·, '1 ;{ ( C. ... T ' l. .., ] -u ~)I .. c.:,
j5 ;:o I ...... O') I ...... ~ .t,. ...... V1 .. kl (S) ...... ...... ...... .t,. ~ ~ .t,. ~ "'() ~ Analyte 2,3,7 .8-TCDD Total TCDD 2,3,7.8-TCDF Total TCDF Toti.lPeCDD Total PeCDF Total HxCDD Tot&l HxCDF Tot.ii HpCDD Tot.ii HpCDP OCDD . OCDP TABLE 2-(continued) ANALYITCAL RESULTS FOR PCDD/F IN SOIL SAMPLES (µg/kg) TEST RUN 5 . INPUT OUTPUf BAT2-CNI-SL2 TR5-CN1-Sl.3 TR5-CN1-SL3DUP TR5-CN2-SL3 0.85 U 2.2 u 1.4 u 2.2 u 2.2 u 4.2 u 3.4 u 4.4 u l.l u J.3 u 2.2 u 1.9 u 36.3 J 1.6 u 1.3 u 2.8 u 6.4 u 4.1 u 3.6 u 7.2 u 93.9 J l.6 u 2.2 u 2.6 u 87.4 7.4 u &.2 u 10;6 u 482 J 1.5 u 2.2 u 3.0 u 1,520 J 8.1 u 11.6 u 12.6 u 793 J 1.9 u 5.7 u 2.8 u 7,400 J 12.4 u 19.2 u 17.0 u 1,420 J 1.9 u 0.71 tr 6.4 u TR5-CN3-SL3 2.0 u 5.5 u 1.3 u 2.2 u 3.7 u 3.0 u 8.8 u 1.34 U 9.4 u 1.8 u 12.4 u 0.48 U 1 ;i ... 0 (J 1. ,, t I, ( 7 ;, I C ] ' I -J '1 g L
i I ..... CJ) I ..... ~ .t,.. ..... U1 (..J rlJ CS) ..... ..... ..... .t,.. ~ ~ --J .t,.. ~ -0 § TABLE . z_ (continued) ANALYTICAL RF.SULTS FOR PCDD/F IN SOIL SAMPLES (pg/kg) TEST RUN 6 INPUT OUTPITT Analyle BAT3-CNI-SL2 BAT3-CNID-SL2 TR6-CN l -SL3 TR.6-CN2-SL3 TR6-CN3-SL3 2,3,7,8-TCDD 0.37 u 0.60 u 1.7 u 3.1 u 0.92 u Toral. TCDD 6.6 3.4 u 1.9 u 1.7 u 2.2 u 2,3,7,8-TCDF 1.7 u 1.2 u 1.4 u 3.0 u 1.4 u Total TCDF 55.1 J 24.3 J I.2 u 0.70 U 1.4 u Total PeCDD 7.7 u 6.6 u 4.0 u 7.4 u 5.0 u Total PeCDF 125 J 155 J 1.5 u 2.1 u 3.1 u Total HxCDD 135 141 6.7 u 7.2 u 7.2 u Total HxCDF 701 I 826 J 1.4 u 1.3 u 2.3 u Tota1 HpCDD 1,930 J 2,660 J 8. l u 8.8 u 9.0 u Total HpCDF 1,260 J 1,540 J 1.9 u 3.7 u 1.3 u OCDD 9050 J 11,200 J 11.7 u 12.B u 11.4 u OCDP J,840 J 2,.550 J 1.1 u 1.9 u 2.3 u y, ;:n ... 0, ~f. ! . C UJ u.., u ~ T ·r r' C': 1-· T r ) "7 I T ~ ' , .. C
~ D Al I .... CJ) I .... tB A .... Vl (.,J I\.) IS) .... .... .... A IS) A ~ A IS) ~ -0 IS) &1 TABLE 2. (continued) ANALYTICAL RESULTS FOR PCDD/F IN SOIL SAMPLES (µg/kg) TEST RUN 7 INPUT OUTPUT Analyle BAT4-CN1-SL2 TR7-CN l-SL3 TR7-CN2-Sl.3 2.3,7 ,8-TCDD 0.94 u 1.2 U Total TCDD 9.7 J 4.3 u 2,3,7,8-TCDF 1.0 u 2.4 u Total TCDF 61.l J 1.4 u Total ~DD 21.l 3.2 U Total PcCDF 134 J 1.8 u Tot.al HxCDD 278 9.0 u Total HxCDF 695 J 2.5 u Total HpCDD 3,690 J 9.7 u Total HpCDF 1,150 J 6.1 u OCDD 10,200 J 15.5 u OCDF 2,670 J 0.62 U Notes: U -Not deleted a{ the level reported. J -Estimated only. Below instrument c::llibration range. TCDD -Tctradtlorinatcd dibenzo-p-dioxin TCDP -Tctrachlorinatcd dibcazofuran -HpCDD -Heprachlorinalcd dibcm.o-p-dioxin HpCOF -Hcpeachlorinaled dibcnzo(uran HxCDD -Hcxachlorin.ared dibcnzo-p-dioxin HxCDP -Hexachlorinatcd dibenzofuran PeCDD -Pentacblorinatcd dibcnzo-p-dioxin PcCDF -Pentacltlorinaled djbcnzofuran OCDD -OctachJorirurted dibenzo-p-dioxin OCDF -Oct;\chlorioated dibcnzofurll(} 1.4 u 3.0 J 1.9 u 1.9 u 8.l u 3.0 u 16.2 1.9 u 18.9 u 2.7 u 22.2 u 1.6 u TR7-CN3-SL3 0.90 u 6.5 u 3.4 u 3.4 u 8.2 u 4.4 u 20.1 2.9 u 21.6 u 3 . .5 u 28.5 u 4.3 u -, t ;r I-Q lj r. c:. u (, (, -, T ;T C rr J ,_ T ' J.. 7 T, ,, ~r I·· G
TOTAL MASS OF PCDDs AND PCDFs EMITTED
TO THE ATMOSPHERE DURING OPERATION OF THE MTTD
Run Number Average Sum of Total Total Amount
and Sample Volumetric Duration of Total Gas PCDD and of PCDD and
Location Flow Rate Run (min) Flow PCDF PCDF Emitted
(dscmm) (dscm) Concentrations to Atmosphere
(ng/dscm) (mg)
Run 1, Outlet 2.06 720 1,483 31,214 46.3
Run 2, Outlet 1.86 690 1,283 65,602 84.2
Assume 1. 66 -Assume 38 ,583 -
Run 3, Outlet Average of 660 1,096 Average of 42.3
Other Runs Other Runs
(Outlet) (Outlet)
Run 4, Outlet 1.36 510 693.6 737 .7 0.51
Run 5, Outlet 1.88 570 1,071.6 96,112 103 .0
Run 6, Outlet 1.31 570 746 .7 18,572.2 13.9
Run 7, Outlet 1.47 540 793.8 19,260.1 15.3
TOT AL MASS OF PCDDs Ai.JW PCDFs EMITTED TO
ATMOSPHERE DURING OPERATION OF MTTD = 305.51mg :::: 0.3g
BCD/047-1127rfOTALDXN.TBL
Table Lt
Summary of PCDD/PCDF Results for Ambient Hi-Volume Filter SaIT1_ples
•. lll~iiiii&ifJB
2,3,7,8-TCDD 1.59c-04 l.19e-06 J
2,3, 7,8• TCDF 8.39e-06 8.13e·07 · 1
Surrogate Recover:,· (%)
13C-2,3,7,8-TCDD 69 65
13C-2,3;7,8-TCDF 74 71
Analj-te
Total TCD)) l.73c-03 B S.14e-05 B,Q
1,2,3,7,8-l'eCDD ' l,23c-03 B 4,63e-06 B,J,Q
Tot.al PeCDD 8.03e-03 B 5.08e-05 B,Q
1,2,3,4,7,8-HxCDD 2.91e-03 B B,J
1,2.,3,6,7,8-Hx<~ 4.27e-03 B 3.S0e-06 B,J
1,2,3,7,8,9-HxCDD 7.79e-CJ3 B 7.81e-06 B,J ·
Total HxCDD 5,78e-lll B 6.56e-05 B
1,2,3,4,6,7,8-HpCDD · -5.78e--02 B,E 2.33e-05 B
Total HpCDD i.18e-01 B,E 5.44e--05 B
OCDD 1.?.3e-Ol B,E,S 9.19e--05 B
Total TCDF 1.77e-04 1 5.50e-06 J,Q
1,2,3,7,8-PeCDF · 4.82e-05 -1.75e-06 u
2,3,4,7,8-PeCDF 1.95e-05 J 1.06e·06 u
Total PeCDF 6.76e-04 I,Q 3.94e-06 J,Q
1,2,3,4,7,8-HxCDF 1.64e-04 I 9.38e-07 u
1,2,3,6,7,8-fu-CDF 8.94e-05 s · l.19e-06 u
2,3,4,6,7,8-HxCDF 9.78e-05 9.38e-07 B,J
1,2,3,7,8,9-HxCDF S.89e-D5 8.75c-07 u
TotalHxCDF 1.55e-03 .13,l 4.69e-06 J,Q
1,2,3,4,6,7,8-HpCD F 1.58e-CJ3 B 1.56e-06 B,J .
1,2,3,4,7,8,9-HpCD f 4.20e-04 B 1.13e-06 u
Total HpCDF 7,85e-03 :s 4,38c-06 B,J
OCDF 5.75e-03 B,S S.38e-06 B,J
Surrogate Recovery (%)
l.3C-2,3,7,8-TCDD 68 69
l.3C-1,2,3,7,8-PcCt)D 93 96
13c.1,2,3,6,1,s~Hx1:oo 90 90
l3C·l.2,.3,4,6,7,8-H 9CDD 113 91
13C-OCDD lU 68
13C-2,3,7,8-TCDF 78 77
Table
(Continued)
,~ir,r"sf.'l' :~\ti/ff' lf~~4h~;~J!!):'~lrili~1~~ji' . "'~&i,{j\l@£'!1 •· -.S •. <:_, _ _.\~-~~
DC-1,2,3,7,8-PeCDF 92 %
MMS Surrog.!te Rcco,·ery (%)
13C-li'.2,3,4-TCDF NA
Qu.ili!lers:
B • Analytc found ~ ~4tcd laboratory niethod blsnk.
C -Oxluting isomer prc5.sc.t.
E • Estimate only; exceeds ,nt.niment c...Ilbration range.
I • Possible pclychknfoated diphenyl ct.her interfencc.
J -Estimate only, 0¢low iro inime111 C!!llbi-atlon range.
NA • Not analyied.
Q • P~k p~nt 011tside io<1 ratio limits.
U -Not dete.ctcd at the !evt I reported.
Hi-Vol Filter Blank valocs e,1IcuL1t0d u.s\ng 3 nominal volume of 1600 ~-
NA
01/19/95 15:06 □PM -REGION IV 002
~002
----~ ............................. . .. ....... -............. , ........ ·---
R E P O R T SUMMARY
SliR-JECTS Hazardous and toxiG w--i:iSte management I .. Transmission nubstation d&Sign
and operation / Distribution substations
!OPICS PGB
Chemical anaJyi:;is
Tr~nsformers
_ ............. ' ........................... ---
Capacitors
PCDF-PCDD
lnsulatlnQ oil
Al JDIENCF Environmental mi:ln~!=lers / Distributicn enginaars
Analysis of Polychlorinated Dibenzofurans
arid Polychlorinated Dlbenzo-p-Dloxlns in
1tansformers and Capacitors
Volumes 1-3
PCDF and PCDD-by•products of PCB pyrolysis and combus"'
t!on-apparently cause many of the health effects originaJly
attributed to PCB. In parallel and round•robfn studl~, indapan-
. dent laboratories found that normal equipment operatio(I and arc-
ing failure cause little if !ilnY oxidation and do not significantly
modify PCB fluid~ .
.. -------. ·-··------·---·' "-·-··--~-... •··•-··--··---··•·······--'.'··•-·---
BACKGROUND f~rtiaJ oxidation of askarets-mlxturn-s of polychlorineted biphenyls (PCB)
and tr,-and tetrachloroMnzenes-produces p01ychlorinated dlbenzofurans
(PCOF) ,md polychlorinaied dibenzo.,p-oToxlns (PCOO). However, ~nalytic
techniques for seµarating t11e active eomponems In these mixtures had not
m~tured priOI" tn this study. Information had also been lnl:5l.l11ident ~m the
qu@.nfity and types of PCDF and PGDD in as-manufactured PCB and on
thA formation of these by-products during normal operat.iu11 or arcing f1;1.ilure
in utility equipment. Because Of tf'lel; .. e ungertalntles, utilities end regulators
~,ave as~umed the worst•~se PCDF;..PCOO formation when ther~ Is a PCB-
related accident, thereby overstating the potential toxicity. EF1~1 report
El~-4858 desC":r1bes portions of the research psrT"ormed in these projects.
OBJECTIVE To improve techniques tor measuring PCOF/PCDD in the pree•nce of PCB,
..... ---.. ----.. ·-........ -..... _ .. ___ .. ___ .. ______ __,_ .. ,, ... , .... __ _
APPROACH Five laboratories (il'lOIUOlng two whose studies are d'iscussed In raport
EL/EA-4858) performed round-robin gas chroma\ogre.,phy-mass spectrome-
try analys .. es of PCDF-PCDD samples using specially prepared carbon-13
(13C) PCDF spiking compounds. Aftt~r the first (tet of analyses, each labora-
tory modrfied its techniques and analyzed a larger group of sample$ from
utilrty equirment. Another organiution statistically analyzed .all th6 labora-
tory r!e?!:;U!ts ----....... _ .......................... ..
Rf:SUL.TS These three volumes report the second group or PCOF--PCOO an~lyses.
Results trorn all participating laMratories correlated rer'r'lal'kably well. Some
of the re.suits follow.
Ol :19 :95
15:[17
[1[13
'6'202 2GO l i2-I
!JF'M -REC3 I !JN I l.)
orerattonsBrAn~h
EPRI
Pl.:RSPECTfV!=
• Ute of the 1~c compo1.mr.is allow~ :;u(:G~ul sr:pamtion nt the com-
ponents in SP.Vera! dos~ly ~lutinl'.} · p~irs c ,t pf¥iiologically active PCDt-'.
:rnd !~~;•active compounds.
• Anal~!;!.S of sample$ trorn ulility equiprnent suggested that the
PCDF-PCDD present · d!d not result from high-load, high-t~mperature
ope:ration
Volmnos 1 and 2 d8sel'ibe :;everal MalyUc t~hniqu~s. wlt!J tha appen-
dix of Volums 2 including a report on th,i 'inalys,s hy the University of
Umea in Sw,;!d1m,.~s wt!!. Volume 3 summari:,:ea A.fl the l:woratory
techniques, presents compreh&nsi~ sta1iStical analyMs, and provfctes
a.n ex~cutive tummary
This researc.h !8 a IRndmark in PCDF-PGDO analysis. Orie important
rP.sult ls tM synthe~is (')f new PCr'.1Fs for llSe as spiking compounds in
gas chromatography-mass spectrometry analysis_ ihe ability to sepa-
n3.te many of the active ~CDF compounds from mor~ innocuous materi-
als is also of great value. The high correlation of results from several
laboratorles indicates that researchers c::an ~X8rclse gtAat flexibility In
selecting technique..~ anrl developing faollltfes.
· PHOJEC1'S RP?-028-7, RP2028-8, RP2028-10
EPRI Project Managers: Gil Addis; JacqtJes Guertln
Flectrical Systems Division; Environmant r)lv!sion
Contracto~: New York St.tte D11partment of Health; Battelle Columbus
l...ahoratorie~; R~search _jtfangle lnstitut~
For furtMr informati(1n on EPRI r~!:earch programs, eall
EPR.1 Technical lnfom1.?-tiot1 SpeciaJims (415} 855-2411 .
01/19/95 15:07 OF'M -

R
EGION IIJ
1-': no 'cM 02 26n 1 7 21
Analysis of Polychlorinatcd Dibenzofurans and
Polychlorinated Dibenzo-p-Dioxins in ·1ranstorm~rs
and Capacitors
vorume 2: Formation of PCDF and PCDD in Askarel and
Contaminated Minernl Oil Equip11~nt
· EUEA-5443, Voluma 2
RP.search Project 2028-S
Final Report, M2rch 1988
BATTFLLE MEMORIAL INSrlTlm:
Battelle Columbus Divisfon
605 King Avenue
Columbus, Ohio 43201-2693
Principal lnve...-.tigaton:
W. M C:nokr.,
r: L. u .. sioos
With contributions frol"I~
l.lMtA lJNlVE:RSITY
Department of Organir. C:hemlstr}'
Um~a, Sweden $-901 137
Pnr:cip_(II lnv~stigator
C R2ppe
fJ reprned fo,
Electric f:Jower He.o;earch· ln::;titute
· 3412 Hillview Avenue
Pelo Alto. CaJifomle 9430-4
EPRI Project Managers
b Addis
fr2nsmiss,on Subst;;tions Pmgr?.rn
flec::ri c:.?.i Systems L)!visi<:;,r.
,,
Land a,1d Weter Oue:.lity Studk<, Progr2In
Environment Division
004
~004
01/19/95 15:08
01 :}9 :95 1..1 :00 '5'211 2 2130 Ji2-!
OPM -REGIOt-~ IlJ 005
t,LsSTRAC i
A $tudy wa s cnr,duct<'•i by fiw, imfr,pendi:>nt labor;o.1.o rii:tS to 1:valu.:ite methods for the
measurement of trice level~ of polychlorinated dttenzofurans (PCDFs) and
pc1ychlorinated d1benzu-p-diox•ins (PCODs) ill uU1 Hy dielectric liqµids. £1,.ch
hboratory @vaTuatfJ,(i a diffai-ent ane.lytical method. The. method evaluated by
6atte11e involved spiking with labelled. internal standards, analyte enrfc:hmMt by
column chromatography, and analysis by high resolut1on gas chromatogrtiphy/hi~h
reso1ut.'ion mass spectrometry {HRGC/HRMS).
Baseline analyses of fiv8 die1ectric fluids 1<1ere concucted by e.i.ch laboratory as an
· initial test of their methods. The variabn ity af results between the t·ive mathod$
was within expectations, and the fiv1, methods were deemed suitable for round robin
evaluat~on. ·
In the round robin enluation, the five methods were used to analyze 10 l1(1Uid
samplesj including seven utility dje1ectric fluids. The liqu1d samples were spiked
· with (lative PCDD/PCDF to estimate accuracy. The Bittel'le results were generally
within 70 percent of the spike v2.1u.~ except for HxCOF which exhibited a strong.
positive bias. This result was considered a~ outlier. ih& Batte11e results were
consistently lowfir than the average resu1ts obtained for the five laboratories.
ov1f111, the methods proved to be both rugged and' reliable when used with labelled
qu antificatinn and recovery stanoards.
Th~ in-service liquids used in this study were found to tia.vere1at1vely low leve ls
CJf PCDDs and trace amounts of PCOF. Liquids from tr&n~-formers with more than 25
years . of service had higher PCDF 1ev~ls t han 1icuids from newer transformers.
l.iquids from utility appliances exposed t o thermal and electrical stresses did not
have • ~1evated PCOD or PCDF 1eve1s. PCDF leve1s increased as the Aroc1or number
(and rP1 ative amount -of c:hlor"ination) increased.
~005
01/1'3/95 15:0E: CH1 -REGION IU
Operst1onsRranch 006
ih·:s sludy pr,iduct:d a qn':~t 2mo,1nt ot insi~hL intc the variabi i it.y of ,;1:i;llytical
;;ii:ithods applied to t..,..,ace 2.Ml_ys·Js in i1 c..omplex <lie1~<:-tric fluid rilalrix. PCB
· constitute the principal class of interferenis for 0odern mass spectrometric
m~t.hods when used to ana1,rzc polych1orinatt:J aromatic s·pecies such PCDF 2nd PCDO.
Sev~tal c:ontlu~ions tan be dr.:i.wn com:i:.rning performance of the mettiodo1ogy and the
acturate screening 6f in-service dielectric fluids.
METHODS
Tha analytical -procedures proved to be both ru99E1d and re1 {able wh~n used w1th
l 2.hP-1l ed quant Hi c.ati on and recovery standards. The quanti fi Ciit ion standards are.
used to calculat.P. errors from extraction a.nd sorbent partitioning 1osses. This 1s
~specially importlnt· in the Askare1 and mineral oil matrix since the high organic
burden found with this matrix requires secondary partitic,ning to remove interfar1ng
PC8 and the background h_ydrocarbons fror:: mineral 01!.
Random outliPrs were observed in ~his study. One example was the elQvated levels
of hpl(;;r.h1orodibeniofuran found in the in-service analy$es. This kind of acute
error can ari~e from a mistake in the ~ravim2tric preparation ~nd dilution of the
l.;,,h elled recovery standard. Ar.other pos sib1e ·cause . for thi$ random error is
se1~ttive part.itio:iing losses cµring sample clea:1 up. Observing this type of
spurinii-, result indicates that the methods should be used with enough quality
control checks to "flag'' this type of error durin9 the ana.1ysis. Using a second
labeled intern2l standard to quantify the mass recov -~ry of the quanti fication
standards wou1d identify this prob1ern if it ,s re·:ated to 'quantification standard
l cJs~.es.
Th~ observed d~ta variability in this program was sm~ller than ths participants had
anticipated before the program bE:gan. In this very difficult matrix, a chlorinated
oi1, most analysts 'would predict a variibility of one to two ord_ers of magnitude
(JOx to JOOx scatter around the true value). In n·,ost cases~ the relative standarci
devia-tions werE' found to be less th2.n 100 percent. The re1ative average dev;ation
is the absolute differellC:e bet,'{een individual results and the mean (or true value),
divided by the numMr of determinations. For sarnp:es such as the Aroc1or 1242,
[¢1006
15:09
1-L 0.1
[H1 -REGIOt'i JIJ
rmerat1onsRranch
007
/\ro<;lor 1016, and miw~rz.1 oil : the :ivera<;1.: deviation was most ofton -le:.~ than 50
jlGrc.r::nt. This mt.ult w,i' S<'t"n in individual laboratury r&()licate anilyses and in
grouped data from different ldboratories.
rn~sERVTCE LJOUID ANALYSES
Th~ in-~Hvice liquids tested ·in -Ulis program were found to have relatively low
amount~ of P[OO in a11 samples tested. This result supports th~ hypothes1s he1d by
mtrny chem, s:ts · who have 1nvestiga.ted Askare1 and PCB-containing fluids that dioxins
.. 1-1-1 not. a rn~.1or con st it.uent of the.se mixtures. E~,ept for the mi nera 1 oils,
rolychlorinated dibenz.ofurans, ilOW8Ver, wore found in trace amounts in a.11 of the
s11mples testect. The mineral · oil samples were found to have extreme1y low amounts
of PCDD/PCOF if any were found at a11. Even the 1n~serv1ce 1 iquid from Tt~an$former
4, a network .oi stdbution transformer that was involved in a high energy excursion,
w,1s : found to have r.11nimal. amounts of PCDD and PCDF. Transformer 4 had visible
carboni ·and major .signs of scorchjng on the case and the area of the· electrodes.
ThP-Askarel transformers with more than 25 years of service tended to have higher
1e-ve1s of PCDF than the appliances put into service fot a shorter time.-rt . is
possih1e that manufacturing controls improved as the production of Askarel matured
in the 1960s sur:h tha.t Askare1 was produc~d with lower 1ive1s of PCOF in the as-
del ive.r11d fluids. rt wou1d be 'interesting to cbtai.n rep1acement A~kare1 with a
known lot number whic.h matched a sample with extended service life. Ana1yzing
sarnplP.s of ;in unused Askarel and cornpcring the PCDF 1e-veh: in a samp1e subjected to
heavy load · and environmental stress for u, extended period wou1d challenge the
theory that otility opetation contributed to eTevatt:d PCDF levels in Askarel fluids
used in tran~fonnQr and capacitor dl)plice.tfons.
Two utility a0pliances wMe se1ectec!-by the EPRI Techrdcal Advisory Committee for
speci a 7 attention. An Askate1 -filled electrostatic precipitator (E'SP) transformer,
and ,m • oil-filled arc furnace transformer. Both of these applications invo1ve
extended thermal 2nd electrical excursions during daily operation. These two
samples were the "~mrst case" for testing service iitress on the die1ectric flu ids.
The arc furnace had essenti a 11 y no PCDF or PCDD, and the PCDF leve1 s ; n the ESP
trons:former appeared to be dictated by the age of the 1in'it ·(27 years of service}
an<l the fluid composition (Aroclor 1260). This extended period of stress did not
appear to elevate the PCDF levi1s above.typic~1 Arciclor 1260 contamination levels,
One capacitor was tested in the in-service 1 iquid ~<.:reeni ng program. · It was -found
to have -relatively low levels of PCDF compared to the ot~ar Askarel~filled ·units.
i4J007
Cll /19/95 1s: rn
-~-.---Q.1..::.J.§!dl5 __ 1-1: 01 'l)'202 2HO 172-l
OF'M -RECiIOH Il)
Op~ratlonsBran~h
C10E:
The obi.erved distr1ht:tinn of PCl)F seemed to fonow a tr~nd t'lf -higher concMtratfons
of PCDF'. ari-::ing \-dth the high~st degree of ch1or~natton Aroclor-·. The Aroclor 1280
with 60 perc.ent chlorine by weight tendad to have hi9her 1eve1s of PCDF" in every
comp!rab1e sample than Aroclor 1242, or Jl.roclor 1016, both of 1-1hich havt
ap~rnxi~ately ~? pertent chlorinP 1n the h~<;e Aroc1or.
A seco_nd 1-'ffed. was obs0tved ,n these dat~, the re1ativ1? conr:entration<; of PCDF
C(mgeners in any ~amp1P tend:-to favor-the ana.loq:; with h ighff ch1orina'tion as the
chlorination number of the underlying Aroc1or ifcreases . For instanc~ the
proportfon of .hex?., hPpta. and octach1orodibentofurans ar~ higher in Aroclor 1260
than Aroc1or 124.?. If PCDF are form~d b,v direct internal condensation with the
addition of oxygen, Ht1 elimination can occur. This reaction would preferantia11y
prnrluce high~r levels of c:h1orinatiori in the produ~t PCDF when high degrees of.
~hlorination occur in the n~adant PCB.
SUMMARY
This ~tudy -was successful · in developing 9 set of methodologies that re11ab1y
d~termfoe trace 1P.ve1s of PCfJF and PCDD in a vei-y d~-fficu1t matrix -~ ch1orinated
organic oil. Tl1e deve1opment of commercially available: reference standards and the
statistical v2.l 1datfon of reforence methods th.it ca;, be used to ana1yz1:: utility
fluid was a mejor contrib~1tii:Jn to the -quality and d~fen:;·ib1lity of d?..t.c 1n this
field. The method v1~rification program sho~1ed that a ran~:e of in:;;tr-umentatfon cen
be ~uci:e~sfu11y _us~d to measure tr.:::ce levels of PCO;;: and PC:.OD 'In utniLy f1u •i ds .
In genera.1, the· methods e:np 1 oyi ng 1 ow reso 1 Ut ion m2ss spectrometty r~quir-e
add it ion al col wnn ch,omatography to i so 1 ate PCDF /PCDD---enriched fr act 1 on for fi na. 1
gas chromatography. The precision Of biino spiked 5arnples 'fias superior to the
variance expected by expErienced 2.nalysts who had pr~viousiy performed this
analysis. Tha avanabilit_y of labelled .quantificattcn standards helped improv(;>
method ptrformance and lower data scatter.
AH.hough the in~service 1 iquids tested in this pro~r!'il 111~re a very 1 'lmitprl set.
there ~,ere interesting findings about the type and d·.stritut:On of po1ych1or1na-ted
dioxin and furan <;pecit?<i in the systems testad. Dioxin ·1Pve1s were vf!ry low~ or
not rneasurab1f: in the l i quids ana1yzed_ The minr.ra1-cil-filled equirment had
1evels that were foum1 onl_v at the quantification lirwits. of the methods emp1oyed.
Aroclor 1260 a~pears to hav~ higher 1eve1s of PCOF with enrichm8nt of the higher
chlorine-number analogs, \--1hen compared to Arocltrr !242, _lOlo. or Aroclors with
few~r ch1 orine atoms per molecule than 1260, This data base can not support the
01/19/95 15: 10
' 01 :HJ :95 '!t202 260 li24
OPM -REG I ot,J I IJ
0DerRt1~n5Brfinch
009
pn?tnise that the <1gi. of Ask;;:rel tn,nsformcrs tend:; to favor hi9hE!r PCDF level·s in
older trcnsformers s,nce only four units were investigated.
@008
■
&EPA
SPEAKER:
TOPIC:
DATE:
TIME:
PLACE:
BRIEFING
Linda S. Birnbaum, Ph.D., D.A.B.T.
Director, Environmental Toxicology Division
Health Effects Resear~h Laboratory
Research Triangle Park, NC
Dioxin Reassessment
Tuesday -October 18, 1994
2:00 p.m.
Auditorium
Environmental Research Center
Research Triangle Park, NC
For Information Contact: Theresa Harris
Research Support .Division/SSTSB
Health Effects Research Laboratory
Research Triangle Park, NC
919-541-1133
-------I IERl-----~--► HEALTH EFFECTS RESEARCH LABORATORY
■
-■------------------■
•,-, ' I ' • ~
-, l)~:;tl;;~11,$fl$.]1z11.:~2Jtl~~i1nf!rs:;~MIWl;;l;;:l;l;#:I
TL-RTP Project: 29600 Method 8290 PCDD/PCDF Analysis (b)
\_) Client Sample: TLI WATER BLANK Analysis File: S945801
Client Project:
Sample Matrix:
TLRTPID:
Sample Size:
Dry Weight:
GC Column:
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-~IxCDD
1,2,3,4,6, 7,8-HpCDD
1,2,3,4,6,7,8,9-OCDD
2,3, 7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4, 7,8-PeCDF
',_., 1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3, 7,8,9-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8,9-OCDF
TotalMCDD
TotalDCDD
Total TriCDD
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
Total MCDF
Total DCDF
Total TriCDF
Total TCDF
Total PeCDF
Total HxCDF
n/a
WATER
TLIBLANK
0.200 L
n/a
DB-5
ND
ND
ND
ND
ND
13.8
EMPC
EMPC
ND
ND
6.3
ND
EMPC
ND
EMPC
11.8
EMPC
ND
ND
ND
EMPC
ND
ND
13.8
EMPC
ND
41.3
EMPC
ND
6.3
Date Received: I I
Date Extracted: 09/20/94
Date Analyzed: 09/25/94
Dilution Factor: n/a
Blank File: S945801
Analyst: JW
5.4
8.9
6.7
5.6
6.1
30.0
7.9
5.1
4.9
3.1
16.0
4.2
9.5
28.8
3.5
5.3
12.4
7.4
8.9
6.1
1
46.7
7.9
1 55.1
7.9
5.0
1 22.3
Continued on next page
Triangle Laboratories of RTP, Inc.
801 Capitola Drive • Durham, North Carolina 27713
Phone: {919) 544-5729 • Fax: {919) 544-5491
Page 1 of2
Spike File: SPM2372S
ICAL: SF53254
CONCAL: S945800
% Moisture: n/a
% Lipid: n/a
% Solids: n/a
1.09 36:09
1.41 32:16
1.ll 36:36
22
M237_PSR v:1.09, LARS 5.13.12
Printed: 15:47 09/26/94
· TL-RTP Project: 29600
(._,, Client Sample: TLI WATER BLANK
Method 8290 PCDD/PCDF Analysis (b)
Analysis File: S945801
Total HpCDF
13C12-2,3,7,8-TCDF
13C12·2,3,7,8-TCDD 13C12· 1,2,3,7,8-PeCDF 13C 12· 1,2,3, 7 ,8-PeCDD
13C12·1,2,3,6,7,8-HxCDF
13C12• l,2,3,6, 7,8-HxCDD
13C12-l,2,3,4,6,7,8-HpCDF 13C12• l,2,3,4,6, 7,8-HpCDD 13C12-1,2,3,4,6, 7,8,9-OCDD
37CI..-2,3, 7,8-TCDD
13C12·2,3,4, 7 ,8-PeCDF
\ ... _) 13C12-l,2,3,4,7,8-HxCDF
13C12-l,2,3,4, 7,8-HxCDD
13C12• l,2,3,4, 7,8,9-HpCDF
13C12-l,2,3, 7,8,9-HxCDF
13C12-2,3,4,6,7,8-HxCDF
13C12-l,2,3,4-TCDD
13C12-l,2,3,7,8,9-HxCDD
11.8
5130
5160
5960
5420
8280
8070
7370
8280
16060
395
6210
6460
7430
9490
7780
8880
1
51.3
51.6
59.6
54.2
82.8
80.7
73.7
82.8
80.3
39.5
62.1
64.6
74.3
94.9
77.8
88.8
21.3
0.77
0.82
1.56
1.43
0.50
1.22
0.44
1.02
0.84
1.54
0.51
1.20
0.44
0.51
0.51
0.82
1.19
Data Reviewer: __ 9h.u..~=-----'G.~=~=-J=-a1t...~ ____ 09/26/94
Triangle Laboratories of ATP, Inc.
801 Capitola Drive • Durham, North Carolina 27713
Phone: [phone] • Fax: [phone]
Page 2 of2
24:06
24:57
28:32
29:41
32:21
33:04
35:10
36:08
39:27
24:58
29:18
32:15
32:59
36:34
33:36
32:52
24:43
33:22
23
M237_PSR v:1.09, LARS 5.13.12
Printed: 15:47 09/26/94
TL-RTP Project: 29600
\....) Client Sample: 942828
Method 8290 PCDD/PCDF Analysis (b)
Analysis File: S945802
Client Project:
Sampie Matrix:
1LRTPID:
Sample Size:
Dry Weight:
GCColumn:
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8,9-0CDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
\_. 1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3, 7,8,9-HxCDF
1,2,3,4,6, 7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8,9-OCDF
TotalMCDD
TotalDCDD
Total TriCDD
Total TCDD
Total PeCDD
Total HxCDD
Total HpCDD
TotalMCDF
TotalDCDF
Total TriCDF
Total TCDF
Total PeCDF
TotalHxCDF
WARREN CO. PCB LANDFILL
WATER Date Received: -09/14/94
88-36-1 Date Extracted: 09/20/94
Date Analyzed: 09/25/94
0.175 L
n/a
DB-5
ND
ND
ND
ND
ND
13.5
69.7
ND
ND
ND
ND
ND
18 .0
ND
5.6
ND
EMPC
ND
ND
ND
8.8
ND
ND
13.5
EMPC
ND
18.5
ND
ND
18.0
Dilution Factor: n/a
Blank File: S945801
Analyst: JW
1
1
1
1
6.3
9.2
8.2
6.8
7.4
4.5
5.6
5.4
4.9
3.9
5.2
8.5
12.9
4.1
6.1
14.3
9.2
7.4
21.2
21.5
8.3
4.5
5.5
Continued on next page
Page 1 of2
Triangle Laboratories of RTP, Inc.
801 Capitola Drive • Durham, North Carolina 2n13
Phone: [phone] • Fax: [phone]
Spike File:
ICAL:
CONCAL:
SPM2372S
SF53254
S945800
% Moisture: n/ a
% Lipid: n/a
% Solids: n/a
1.03
0.84
1.19
1.06
60
36:08
39:27
32:52
35:10
B_
B_
B_
B_
B_
M237_PSR v:1.09, LARS 5-13.12
Printed: 15:47 09/26/94
'
TL-RTP Project: 29600
0 Client Sample: 942828
'-'
Total HpCDF
13C,2-2,3,7,8-TCDF
13C1r2,3,7,8-TCDD 13C12-l,2,3,7,8-PeCDF
13C,2-l,2,3, 7,8-PeCDD
13C12-l,2,3,6,7,8-HxCDF
13C,2-l,2,3,6, 7,8-HxCDD
13C1rl,2,3,4,6,7,8-HpCDF
13C,2-l,2,3,4,6,7,8-HpCDD
13C12-l,2,3,4,6,7,8,9-OCDD
37C~-2.3,7,8-TCDD
13C,2-2,3,4, 7,8-PeCDF
13C12-l,2,3,4, 7 ,8-HxCDF
13C12-1,2,3,4, 7,8-HxCDD
13C1r 1,2,3,4, 7,8,9-HpCDF
13C,2-l,2,3, 7,8,9-HxCDF
13C,2-2,3,4,6,7,8-HxCDF
13C12-1,2,3,4-TCDD
13C12-l,2,3, 7,8,9-HxCDD
5.6
(i(}30
5520
6670
6450
8270
8210
7310
8310
16960
521
7290
6930
8200
10180
8330
9060
1
Method 8290 PCDD/PCDF Analysis (b)
Analysis File: S945802
52.8
48.3
58.4
56.4
72.4
71.8
64.0
72.7
74.2
45.5
63.8
(i(}.7
71.7
89.1
72.9
79.3
0.78
0.80
1.50
1.55
0.51
1.22
0.44
1.02
0.85
1.53
0.51
1.21
0.44
0.50
0.51
0.80
1.22
24:05
24:56
28:31
29:40
32:20
33:03
35:09
36:07
39:26
24:57
29:18
32:14
32:59
36:34
33:35
32:51
24:41
33:22
Data Reviewer: --~.......a., .... &=>-..;;.--..;.;:~=-=-4.;'-------09/26/94
Page 2 of2
61
M237_PSR v:1.09, LARS 5.13.12
Triangle Laboratories of RTP, Inc.
801 Capitola Drive • Durham, North Carolina 2n13
Phone: [phone] • Fax: [phone]
Printed: 15:47 09/26/94
United States
Environmental Protection
Agency
Communications, Education
and Public Affairs
1702
September 23, 1994
&EPA Activities . Update SPECIAL
EDITION
. •. . . . . _... . ; . . -. .
EPA Seeks New Data To Complete
Draft Reassessment of Dioxin
On September 13, EPA issued a sweeping call to scientists, industries, state and local governments, public interest groups, and
hospital facilities across the nation for new data on dioxin. The call-in is designed to provide additional data for the draft reassessment
of dioxin, which became available for public and scientific review on September 13.
The reassessment to date is the result of EPA's three-year scientific review, the most exhaustive scientific review of a single
compound ever undertaken by the Agency. While it expands the Agency's understanding of dioxin toxicology, the reassessment
is not yet complete and is not expected to be so until late 1995, after scientific peer review.
,.
Speaking before a group of EPA constituent groups, Assistant Administrator for EPA 's Office of Prevention, Pesticides and Toxic
Substances, Research and Development, Dr. Lynn Goldman, M.D. made the following statement:
Today the EPA is releasing a "public review draft" of its dioxin
reassessment. This release marks a major milestone in our
effort to reevaluate our scientific understanding of dioxin.
More than 100 EPA and outside scientists have worlced for
overthree years to develop the current draft of the reassessment.
Over the next 120 days, the EPA will be taking public
comments on the draft document. Early in 1995 EPA's
Science Advisory Board (SAB) will conduct a formal scientific
peer review. We will conclude the reassessment aoout a year
from now, incorporating appropriate changes that have been
indicated by the public comments, peer reviews and the SAB.
Dioxins are a group of chemical compounds inadvertently
created through a number of activities including: combustion,
certain types of chemical manufacture, chlorine bleaching of
pulp and paper, and other industrial processes. Dioxin is
produced in very small quantities compared to other pollutants
(around 30 pounds annually); however, because it is highly
toxic, it has been treated as asignificantenvironmental pollutant
since the early 1970's. EPA first took action against dioxin
regarding the herbicide 2,4,5-T in 1979. Since then, EPA has
expanded its dioxin control efforts of its major programs.
In 1985 EPA published a scientific review of the health effects
of 2,3,7,8-TCDD, the most toxic of the dioxin family of
compounds. That assessment serves as the scientific basis for
dioxin risk estimates for all EPA programs. Since 1985 a
number scientific and newspaper reports have raised questions
aoout the risks posed by dioxin. The draft study not 9nly
updates the 1985 document, but also represents an ongoing
process to build a broad scientific consensus on dioxin's toxic
effects.
To help foster this consensus, EPA has worlced to make each
phase of the dioxin reassessment an open and participatory
process. These efforts have included the involvement of
outside scientists as principal authors of several chapters,
several public meetings to take comment on our plans and
progress, and publication of earlier drafts of our work for
public comment and review. We are continuing this
participatory process by making the current draft available for
public comment and full scientific review. When this process
is completed, we anticipate having an up-to-date and thorough
scientific assessment of dioxin that is at the cutting edge of
environmental toxicology.
Regarding health risks, the draft study reaffirms the association
of dioxin and cancer.· In its 1985 assessment, EPA concluded
that dioxin is a proven animal carcinogen and a probable
human carcinogen. Today's report reaches that same
conclusion, but with greater confidence. Based upon ooth
animal and human evidence, EPA's estimate of dioxin's
cancer potency is essentially unchanged from that of 1985.
The draft reassessment differs significantly from the 1985
document in its evaluation of dioxin's non-cancer effects.
Today we have a stronger oody of evidence to suggest that at
some dose, dioxin exposure can result in a number of non-
cancer health effects in humans. The effects may include
developmental and reproductive effects, immune suppression,
and disruption of regulatory hormones. We have no direct
evidence to show that any of these non-cancer effects occur in
humans at everyday levels of exposure. However, we can infer
from the data that average everyday exposures are close to
exposures that are known to cause such effects in laooratory
animals.
The draft study also identifies dioxin sources that are known
to contribute to environmental contamination. Waste
combustion accounts foraoout95% of all the known emissions,
with medical and municipal waste combustion dominating the
combustion sources. It is likely that there are a number of
unidentified sources of dioxin in the U.S. and that we do not
have sufficient information aoout emissions from known
sources to provide precise estimates. It is also possible that
much of the dioxin that contributes to human exposure results
frorri past dioxin emissions recirculating in the environment.
Although there are some natural· sources of dioxin, such as
forest fires, it seems clear that dioxins are primarily a product
of modern industrial society.
(J0_ Recycled/Recyclable rr <'\ Printed on paper 1hat contains V7H ,., iaMt !50'JI. l1ICllded fiw
EPA AcLivilics Updalc -Scplcmbcr 23, 1994 · ,~i-; Page 2
We believe· that the pathway for exposure to humans is
primarily via airborne dioxins that settle on plants, and that are
passed on through the food chain ahd associated particularly
with fat. The federal government emphasizes that the benefits
from a balanced diet far outweigh any theoretical risks from
dioxin exposure.
Whilethereassessmenthasbeenunderway,EPAhascontinued
to move forward in implementing its dioxin control programs.
EPA has taken action under every one of its major statutes to
control the risks of dioxin, and we believe these activities have
make, and will continue to make, major strides in reducing
dioxin emissions. Recent actions taken by EPA include
proposing air emission standards for municipal waste
incinerators, proposing stringent water effluent standards for
pulp and papermills and waste incinerators. No laterthannext
February, EPA will propose strict air standards for reducing
dioxin and other emissions from medical waste incinerators.
While the science of the reassessment is undergoing peer
review, EPA will _ be examining the reassessment's policy
implications to determine what changes, if any, are needed in
existing programs. I want to stress that existing EPA efforts
and programs will not be changed on the basis of this draft
reassessment, however, they may change significantly after
the completion of the peer review. EPA is committed to
developing an agency-wide strategy for managing dioxin
risks, concurrent with completion of the dioxin reassessment.
As with the reassessment, we want to provide an opportunity
for early public input into our policy evaluations. This spring,
EPA will hold dioxin policy workshops to explore the policy
implicatio·ns of the reassessment. The details of these
workshops will be announced later.
This massive scientific effort has made it clear that there are
significant data gaps that are critical to our understanding and
effective management of dioxin. As a consequence, EPA has
begun a majorinitiative to expand the understanding of dioxin
sources, environmental pathways and human exposure. Our
highest priority will be_ to identify additional data to improve
the reassessment; however, the exposure initiative will extend
beyond the reassessment into future years.
As a part of this effort, today we are calling on all parties to
voluntarily submit any data that can help us better understand
dioxin exposure. The EPA is requesting that industry, public
interest groups, state and local governments, academia, and
hospital facilities examine their files for existing data. We
need information on dioxin sources, releases and levels in air,
water, soil, food, animal feed, and human tissues. In addition
to this voluntary call-in of existing data, EPA is calling on
industries that are potential dioxin sources to voluntarily work
with the Agency to devise and implement emissions testing
programs.
The reassessment represents a major expansion of EPA's
scientific understanding com pared to ourprevious assessments
of dioxin toxicology. Because many of the studies included
in the reassessment have only recently been part of the
scientific literature and our integration of this evidence is
entirely new, it is important that the reassessment undergo
thorough public and scientific peer review. At the same time,
because the general thrust of the reassessment is consistent
with our past scientific basis, we feel confident in aggressively
pursuing our ongoing dioxin control efforts. This report, once
it has completed peer review sometime next year, will give us
the best scientific basis possible to guide our continuing
efforts to curb dioxin risks.
The draft reassessment consists of six volumes and totals over
2,000 pages. For copies of the draft report, contact CERI/
ORD Publications Center, U.S. EPA, 26 W. Martin Luther
King Drive, Gncinnati, OH 45268, orcall 513-769-7562; or
fax your request to 513-569-7566.
For information on providing comments, readers can refer to
the September 13 Federal Register notice on this action. For
copies of the Federal Registernotice, contact Harold Hammock
at 202-260-4956.
NOTICES PUBLISHED IN THE FEDERAL REGISTER
September 12
PROPOSED 40 CFR Pan 60. Standards of Performance for New Stationary
RULE Sources; Volatile Organic Compound (VOC) Emissions from the
5068-3 Synthetic Organic Chemical Manufacturing Industry (SOCMD
Wastewater.
FINAL
RULE
5065-3
40 CFR Part 52. W ASIDNGTON SIP. Approval to Implement
an Emission Statement Program for Stationary Sources Within the
Vancouver Air Quality Maintenance Areas and the Central Puget
Sound Ozone Nonattainment Area.
PRO POSED 40 CFR Part 52. WASHINGTON SIP. Approvalto Implement
RULE
5065-4
FIN AL
RULE
5068-9
NOTICE
5070-6
FIN AL
RULE
5063-6
FIN AL
RULE
4909-8
NOTICE
4909-3
an Emission Statement Program for Stationary Sources Within the
Vancouver Air Quality Maintenance Areas and the Central Puget
Sound Ozone Area.
40 CFR Pan 52. OHIO SIP. Removal of Approval of two
Exemption Requests for Toledo and Dayton Ozone N onattainment
Area.
September 26 & 27 Open Meeting of the Committee on Hazardous
Waste Identification.
40 CFR pan 52. TEXAS SIP. Approval of Revisions Addressing
the Carbon Monoxide Plan for El Paso.
40 CFR Pan 185. Benomyl and Trifluralin; Reinstatement of
Food Additive Regulations.
State FIFRA Issues Research and Evaluation Group (SFIREG)
Working Committee on Water Quality & Pesticide Disposal;
September 29-30 Open Meeting.
I •
I I I
~-I
l
NEWSLETTER ENVIRONMENT
DOW CHEMICAL IMPLICATED IN
BREAST IMPLANT SUITS
Two Michigan law firms have filed
a motion to bring Dow Chemical
back into the breast implant issue.
One firm, Sommers, Schwartz, Sil-
ver & Schwartz, says Dow has re-
fused to participate in settlement
talks, even though Dow Coming
has agreed to contribute to the glo-
bal settlement fund. Dow Chemi-
cal says it is not liable for Dow
Coming's actions. The law firm
says new evidence of Dow Chemi-
cal's involvement will be present-
ed this month in a case brought by
a woman who opted out of the glo-
bal settlement. Included will be
documents that show Dow Coming
and Dow Chemical knew about the
health effects of silicone, the firm
says. It also says results of early
testing were concealed.
JAPAN STUDYING WAYS TO
RESOLVE DISPUTES
Japan Chemical Industry Associa-
tion is studying the creation of an
organization that would mediate
disputes arising from accidents
that are caused by the use of
chemical products before they be-
come lawsuits. Anticipating imple-
mentation of a Japanese product li-
ability law next July, the move is
intended to help provide out of
court settlements of disputes and
to avoid time-and cost-consuming
litigation. Under the proposed
product liability law, in the event
of accidents resulting from defec-
tive products the damaged party
will be able to seek compensation
from the manufacturer on the basis
of the defective product rather
than manufacturer negligence.
The law will be an exception to the
principle of liability arising from
negligence under present civil
law.
CANADIAN GOVERNMENTS
JOIN FORCES
Federal and regional agencies in
Canada have agreed to a single
administration and enforcement of
regulations under the Canadian
Environmental Protection Act and
the pollution prevention provisions
of the federal Fisheries Act. The
provisions include the Pulp and
Paper Effluent Regulations. In-
dustry will now deal with both
levels of government through the
Saskatchewan Environment and
Resource Management. Accord-
ing to the Ministry of the Environ-
ment, each level of government
retains its own authority but in-
dustries will be able to meet fed-
eral and provincial requirements
by reporting to local government.
In July, the Canadian Environ-
ment Ministry signed a coopera-
tive agreement with Ontario to
set environmental priorities in
the Great Lakes.
AWD TO REMEDIATE
GOVERNMENT SITES
A WD Technologies (Rockville,
MD), a Dow subsidiary, has been
contracted to remediate hazard-
ous waste sites owned by the U.S.
Army, Air Force, and Department
of Energy in Kansas City. A WD
has agreed in the $SO-million con-
tract to perform on-site source
control, contaminated soil remov-
al, and installation of groundwa-
ter treatment systems, and to up-
grade existing water and waste-
water treatment facilities.
USDA RISK OFFICE GETS
INDUSTRY SUPPORT
Chemical and other manufactur-
ers are rallying to support legisla-
tion to create an office of environ-
mental risk within the U.S. Depart-
ment of Agriculture (USDA). The
House last week was to begin con-
sidering a bill to reorganize the
USDA that includes a new office
to conduct environmental risk as-
sessments and cost-benefit analy-
ses of government regulations.
Chemical Producers and Distribu-
tors Association (Alexandria, VA)
president Warren Stickle is lead-
ing industry in an effort to fight
opposition to the provision and to
ensure it remains in the final ver-
sion of the bill.
DIOXIN REPORT DISPUTED
EPA's dioxin risk reassessment
fingers cement kilns as a "major
contributor" of dioxin emissions,
a statement the industry calls·
"inaccurate." The Cement Kiln
Recycling Coali-
tion (Washing-
ton) says that
conclusion is
based on worst
case testing data,
even though the
group sent EPA more representa-
tive data that contradicts the re-
port's conclusions. A rival hazard-
ous waste incinerator group, the
Association for Responsible Ther-
mal Treatment, says the report
highlights the need for more strin-
gent regulation of kilns. Specifi-
cally, the group calls for public
hearings on cement kilns and a re-
quirement for final permits; ce-
ment kilns currently operate under
interim status permits.
CHEMICAL HAZARD BOARD
GETS A NEW MEMBER
In an apparent bow to industry de-
mands, President Clinton will
nominate a 25-year chemical in-
dustry veteran to the federal
Chemical Safety and Hazard In-
vestigation Board. Isadore
Rosenthal spent the first 25 years
of his career with Rohm and Haas,
serving as director/safety, health,
environmental affairs, and product
integrity. Since retiring in 1990 he
has served as a senior fellow at
the Wharton Risk and Decisions
Processes Center at the University
of Pennsylvania. The Clean Air
Act-mandated Board has been
without members until this sum-
mer.
AKZO NOBEL'S FIRST
ENVIRONMENTAL REPORT
In its first corporate environmental
report Akzo Nobel says that in 1993
it released 1,800 m.t. of organic
compounds into treatment works
and 294 m.t. to surface water;
21,028 m.t. of organic compounds to
air; 16,347 m.t. of particulates to
air; 11,132 m. t. of hazardous waste
to landfill; 18,544 m.t. of hazwaste
to internal incineration; 24,033 m .t.
of hazwaste to external incinera-
tion; and 16,605 m.t. of hazwaste to
other methods of disposal. Akzo
Nobel says that "the figures in the
1993 [report] should primarily be
used for reference purposes. Fig-
ures for comparison will be includ-
ed in forthcoming reports."
October 5, 1994 CHEMICALWEEK 41
I NEWS EUROPE/MIDEAST
Amoco nears decision on
European polypropylene project
Following a global review of its
polypropylene (PP) strategy, Amoco
(Chicago) is in the final stages of a
feasibility study for a grassroots 155 ,000-
m. t./year PP project in Europe, where
the market is growing at 6%-8%/year
and the business is again profitable.
Pending approval of the strategy, man-
agement sanction will be sought for a
plant at Geel, Belgium that would come
onstream in late 1996 or early 1997 at a
cost of about $125 million. It will use
the Amoco-Chisso gas-phase, stirred-
bed reactor process in operation at
Amoco's 136,000-m.t./year PP plant at
Chocolate Bayou, TX.
Plans for a new PP plant at Geel were
announced in 1992, but the downturn
in the industry and a major restructur-
ing within Amoco put the project on a
back burner. Propylene feedstock sup-
plies were secured some time ago, and
agreements are still in force.
Amoco, best known for its global
purified terephthalic acid position, also
views PP as a core business and is
Environment
French Academy J'.etiuffs
EPA dioxin report
In stark contrast to the recent 2,000-
page EPA dioxin report, which stresses
the potential health risks of dioxins, the
French Academy of Sciences and its
Committee of Applied Sciences
(CADAS; Paris) have published their
own 80-page study, which states, "Con-
trary to popular opinion, there is no
evidence to suggest that dioxins and
their related compounds constitute a
major risk to public health."
According to Pierre Fillet, director
of CADAS, "Scientifically, our report
and EPA's are very much in agreement.
Where we differ is in the conclusions
we draw from very similar data." He
says that while EP A's conclusions stress
the potential toxicological effects of di-
oxins-and in speculative language that
could inflame public opinion-
CADAS's stress the known toxicologi-
cal effects and how to practically min-
imize them.
The CADAS report concludes that
"PCDD/F [dioxin and its analogs) toxic-
ity in man is infrequent and not seri-
ous." It says that "no fatal case of poi-
soning by these products has ever been
reported" and that "the only clearly
18 CHEMICALWEEK October 5, 1994
interested in expanding in the sector in
the U.S., Europe, and the Far East. But
while the company has a strong posi-
tion in the U.S., with about 1 million
m.t./year of capacity, its presence is
small in Europe and nonexistent in
Asia/Pacific.
Amoco's European PP capacity is
200,000 m.t./yearatGeel. The new plant
will push the company's total in Eu-
rope to 355,000 m.t./year, well behind
Montell, the Shell-Himont joint ven-
ture, which should start operating with
1.2 million m.t./year of capacity in
Europe. Amoco, however, is looking to
grow further, either through grassroots
investment or alliances and acquisi-
tions. The company discussed a joint
venture marketing deal with DSM
(Heerlen, the Netherlands) but settled
for a straight licensing agreement (CW,
Sept. 14, p. 10). DSM's plant is expect-
ed to come onstream the same time as
Amoco's.
NAT ASHA ALPEROWICZ
established effect on human health is
chloracne ... [which is) not life threat-
ening." The study argues that the pub-
lic's "exposure to dioxins is in decline"
and that "current exposure is well be-
low the daily acceptable dose" (DAD)
set by the World Health Organization
(WHO). CADAS says that WHO's hu-
man DAD of 10 picograms/kg/day
"seems today a prudent and realistic
guide to be retained and used for the
management for the risk of dioxins to
public health." Greenpeace says the
WHO level "is 1,670 times greater than
the current U.S. EPA [proposed) stan-
dard of 0.006 picograms/kg/day."
CAD AS says dioxin emissions should
be reduced further, mainly by encour-
aging more sophisticated incineration
of municipal and hospital wastes-
which represent 95 % of known dioxin
emissions.
AT THE SOURCE. According to Hugo Le-
ver, director general of the European
Chemical Industry Council, "The French
Academy report reinforces the Europe-
an Union policy of directly controlling
dioxin emissions at the source, com-
pared to U.S. measures, which focus on
controlling exposures to dioxins."
MICHAEL ROBERTS
Austria
OMV-Repsol link in sight
OMV (Vienna) chairman Richard
Schenz says a 50-50 joint venture be-
tween its polyolefins subsidiary, PCD,
and Repsol's (Madrid) polyolefins oper-
ation is likely to take place in 1995 (CW,
Sept. 14, p. 17). "We are talking tooth-
ers," says Schenz, "but the talks with
Repsol are the most advanced. There is
more than a 50% chance that something
will come of them."
Schenz also reports that there are
parties in Europe and the U.S. that are
interested in taking a stake in fine chem-
icals maker Chemie Linz. Schenz be-
lieves in the potential for "good develop-
ment" in fine chemicals and wants OMV
to maintain a stake in the company while
shedding operative control.
Meanwhile, the performance of trou-
bled agrichemicals and melamine sub-
sidiary AgroLinz Melamin has picked
up sufficiently to allow Schenz to fore-
cast a profit for 1994. OMV is to hold on
to the company for "the next five to ten
years."
GERRIT WIESMANN
in Monte Carlo
Petro,hemi,als
'I; ' ~ ~ ,tt NORSK HYDRO,
QGPGIN ~DC VENTURE
Norsk Hydro (Oslo) and Qatar Gen-
eral Petroleum Corp .. (QGPC; Doha)
have completed/a feasibility study
~-and have signed a letter of agreement
to set up a joint venture to produce
""etffyl~ne'dlchiorfde (EDCJ. The linkup,
in which QGPC . is expected to hoJd
.51'%, is plc1nned,to produce ;400,090
'm.f:o/yearof EDC at Umm Said, initial-
ly fqr .expo1rt to Asia. 1n;t1:ie ft,1ture ttw
partners may build downstream units
for.vinyl c,!:ltoride monomer and polyvi-
nyl chloride:,.:. .,I , "0·
Ethylene feedstock is expected to
bEl purchate,d. tr?m Q9t?ir Peioph~~-
ical Co.~ (Qapco), a joint venture of
QGPt, EniChem, ~aQd ,EIL Atochem.·
Qapco~isf raisi'ng ettlylene !capacity
from 33P,OOO .m.t./year to 525,000
mf·/year 'and·,,c:tqubling low-de,nsity
polyethylene capacity to 390,000 m.t./
year. Chlorine will' be imported.
Norsk Hydro and QGPC are partners
in Qatar Fertilizer .. Co. (Qafco), which is
increasing its U(ea capacify"bY 2,000
m.t./day. The existing 'complex is de-·
signed to produce 2,500 m.t./day of
urea: "" ' " NA
-. r
-MBMORANDOM
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, O.C. 20460
' OFFICE a: REGIONAL OPERATIONS
ANOSTATEILOCAL RELATIONS
.: ,,
Sept~aj:>er 1?',~ 1994 \It
SUBJECT: ~eas~~~•~,,,~~af~, ReasSessment ).~ .§'
FROM: _ Ma~~~ei~ ·.. I tf ' · ·
. ~~·ications Coordinat . · · · . ,~.t .· • ·
·. TO: State Agricultural Officials ·,
-, Intergovernmental Associations ,.\~ .__ ~-~. : -i '
••
1 ·other In~e-~~sted Parties . · __ '·VU ¥ _ :\J',,
Today, · EPA '~~leased ·.for public . l'.evi~w its draft ·· reassessment · ·of
dioxin human health risks. The draft reassessment is the result :of
-over three years of effort ·involving hundred~ of scientists ·from
both inside and outside of government.-The study consists· of two ,_·.
rep·orts, each comprised of three volumes, · and totals over 2000
pages. The reassessment documents are scientific documents ·and the
toxicology of ·. dioxin . · is addressed within ·. the· ·volumes, · and,·
therefore, do not address questions of dioxin policy or regulatory _·,-• -
.. -action., -. There, is a 120 day review period., -. :; : _ : ' r ·· · ·· · .,
·,_.✓ .. _· _.·,;-". __ : _ _.·.-_·?·-_. ·:-···.,._,_:· .. :.:_··<···.'./·'··,:· _:-·_·_,_: .--.··:0::·
Enclosed, please find .the press materials .used today. ·Please also ·
·note that _if· you. require the fµil-' set of volumes, you ·may use _the .:
order _sheet ~nclo_sed ·in the press materials.!'. · · · · · _,'' · ·
' . . .
'.
. ... '
.. ; , . ·,:\ ' .. -..
:: . , ... i ,,_.-__ <
.cl
Printed on Recycled Paps,
UNITED STATES ENVIRONMENTAL PROTECTION AGEN
WASHINGTON, D.C. 20460
SEP 29 1994
MEMORANDUM
:I::ocr 4 1994 ~
OFFICE OF REGIONAL OPERATIONS AND STATE/LOCAL RELATIONS
Reassessment Documents
TO: State Hazardous Waste Officials
Please find enclosed the EPA's recent announcement regarding
the release of the DRAFT Dioxin Reassessment Documents which
occurred earlier this month. The press package includes our press
release, Dr. Lynn Goldman's announcement and fact sheets which
describe the types of information included in the 2,000 page, six
volume set of documents. On the last page of the package you will
also find an order sheet for your use should you wish to order any
or all of the documents. The external review process began on
September 13 and will end after 120 day re~iew period. The Agency
is inviting your comment on the draft documents.
I have been asked by our Superfund program to forward this
information to you and hope it be useful. If I can provide you
with assistance or additional information, please call me at
[phone].
Attachment
Printed on Recycled Paper
United St3tes
Environmental Protection
Agency
Commun,cat,ons. Education.
And Public Atta1rs
(1703)
Environmental News ..
l'OR ULEASZ : . · -'1'0BSDAY, SEPT . 13, 19 9 4
ZPA CALLS l'OR . NEW DIOXIN DA'l'A TO COMPLZTB _ UASSZSSMEN'l'
PROCESS
Luke C. Hester 202-260-1-383
The U.S. Environmental Protection Agency today issued a
sweeping call to scientists, industries, state and
localgovernments, _public interest groups, and hospital facilities
across the nation.for ne~ data on dioxin~ The ncall-in" is
designed to provide additional data for the draft reassessment of
dioxin, which became available today .for public and scientific
. '.
·review.
EPA Assistant Administrat_or Lynn Goldman, M.D. ,· said that
while the Agency's reassessment· represents the collection and
analysis of extens·iv.e scientific data, "This massive scientific ·
effort has made it clear that there still are significant data
gaps that are critical to our understanding of dioxin.· The new·
data call-in is aimed at filling those data gaps in order to·
better manage diqxin and protect the public's health.n
. Goldman noted that some sources of dioxin in the.· United
States may yet be unidentified and that the Agency lacks . .
sufficient information ·about emissions from known sources to ·:
. provide precise estimates, thus pr9mpting the .• call for more . data.:
She also said the Agency is calling on potentiai_industrial dioxin
. sources t(? voluntar1ly .work with EPA to_ develop emissions testing
programs. . . -
. . The reassessment to aate is the result. of EPA' s three-year
scientific review, the most exhaustive scientific review of a .
single compound e·ver undertaken . by the Agency.· While it expands
the Agency's understanding of dioxin toxicology, the reassessment
is not· yet complete and is not expected to be so until late 1995,
after scientific peer review.
R-215(more)
-2-
The draft reassessment reaffirms the link between •dioxin and
cancer and concludes that dioxin exposure at some level may result
in a number of non-cancer health effect~ in humans~ It also
· identifies sources of dioxin known. to contribute to environmental
contamination.
Dioxins are a group .of chemical compounds inadvertently
produced through a number of activities including: combustion,
certain types of chemical manufacturing, .chlorinated bleaching of
pu~p and paper and other indust_rial processes •
. ·Over the next 120 days,· EPA . will be . taking public. comments on
the draft_ document~ Early in 1995,.the Agency's Science Advisory
. Board (SAB) will conduct a formal scientific peer review. ·The ; .
Agency will conclude. the reassess·ment l~ter· in 1995 . incorporating
appropriate :~hanges that ·have been indicated by the public
comments · and the SAB review~ · ·
' \'
·During the scientific reassessment pro~ess, EPA is continuing
its ongoing efforts· to reduce sources of ·1 dioxin through the
implementation . of ·.the major environmental laws. When completed,
the dioxin· ~eassessment will serve as the s·cientific . basis· for
. further -dioxin policy and program development. However, Goldman
said that existing EPA efforts and programs will not .be changed on
the basis ._of :the. draft reassessment. ,: ... , · .. ·'.,·:i -·
/. __ , • ~. -~'.-•:,:.:.: __ , _ _.,: __ .:••r.--•-~-.• • •· !/·• •. ~ '! .:.·• ••,; ·,, •'
'The Agen-c/ has .,already propos'ed rule1s· to .dramaticaily' limit '
dioxin emissions from municipal waste incinerators and is expected
·shortly to .issue similar. rules for hospital .waste .incinerators"".-,
both major sourc::es of ~ioxin. emissions. · · ·
'·.. -: . ~ -~: . , ·_ -; . _-. --. _: ·. ·. :;: ·. : .-·_. ~_-: ..... ': ·:: . ' : .. . -. . . , .. ' .. . -;· . . . . -........ ,. .
· · ·. --:. The· draft reassessment ·!Consists of six· volumes and .totals
. over ·2, 000 pages -._. It is .a scientific .. report _dealing with .· both, .. ;
cancer and non-cancer toxicological: effects,. known :.sources .of.·_ ..... .
·. dioxin in the · environment . and ·currerit ·1e·vels . of human . exposure~.: : ·,' '> : ! :
. ~-Ai / :j \ i • .•· ·.·. ·• ; ; ·:){t ·•• {):[\ \t'.,t'tt:~.\?!( • ,., :'•f :<>\ \ : . • .·
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&EPA
United States
Environmental Protection
Agency
Communications, Education,
And Public Affairs
(1700)
· STATEMENT OF LYNN GOLDMAN, M.D ..
September 1994
ASSISTANT ADMINISTRATOR FOR PREVENTION,
PESTICIDES, AND TOXICS
SEPTEMBER 13, 1994
Today the EPA is releasing a "public review draft" of its dioxin
reassessment. This release marks a major milestone in our effort to
reevaluate our scientific understanding of dioxin. More than 100
EPA and outside scientists have worked for over -three years to
develop the current draft of the reassessment. Over the next 120
days , the EPA will be taking public comments on the draft document.
Early in 1995 EPA's Science Advisory Board will conduct a formal
scientific peer review. We will conclude the reassessment about a
year from now, incorporating appropriate changes that have been
indicated by the public comments, peer reviewers and the SAB.
Dioxins are a group of chemical compounds inadvertently
created through a number of activities including: combustion,
certain types of chemical manufacture, chlorine bleaching of pulp
and paper, and other industrial processes. Dioxin is produced in
very small quantities compared to other pollutants (around 30 ·
pounds annually); however, because it is highly toxic, it has been
treated as a significant environmental pollutant since the early
1970's .. EPA first took action against dioxin regarding the herbicide
2,4,5-T in 1979. Since then, EPA has expanded its dioxin control
efforts to each of its major programs. ·
In 1985 EPA published a scientific review of the health effects of
2,3,7,8-TCJ?D, the most toxic of the dioxin family of compounds.
That assessment serves as the scientific basis for dioxin risk
estimates for all EPA programs. Since 1985 a number of scientific
and newspaper reports have raised questions about the risks posed
by dioxin. The draft study not only updates the 1985 document, but
also represents an ongoing process to build a broad scientific
consensus on dioxin's toxic effects.
To help foster this consensus, EPA has worked to make each
. phase of the dioxin reassessment an open and participatory process.
These efforts have included the involvement of outside scientists as
principal authors of several chapters, several public meetings to take
commenf-on our plans and progress, and publication of earlier drafts
of our work for public comment and review. We are continuing this
participatory process by making the current draft available for public ·
·. comment and full scientific review. When this process is completed,
we anticipate having an up-to-date and thorough scientific
assessment of dioxin that is at ~e cutting edge_ of environmental
toxicology.
·.Regarding health risks, the draft study reaffirms the
association of dioxin and cancer~ In its 1985 assessment, EPA
concluded that dioxin is a proven animal carcinogen and a probable
human carcinogen. Today's report reaches the same conclusion, but
with greater confidence. Based upon both animal and human
· evidence, EPA's estimate of dioxin's cancer potency is essentially
unchanged from that of 1985.
· The draft re~ssessment differs significantly from the 1985
document in its evaluation of dioxin's non-cancer effects. Today we
have a stronger body of evidence to suggest that at some dose,
dioxin exposure can result in a number of non-canc~r health effects
in humans. These effects may include developmental and
reproductiv.e effects, immune suppression, and disruption of
regulatory hormones. We have no direct evidence to show that any
of these non-cancer effects occur in humans at everyday levels of
exposure. However, we can infer from the data that average ·
. everyday exposures are close to exposures that are known to cause
such effects in laboratory animals. ·
The draft study also identifies dioxin sources that are known to
contribute to environmental contamination. Waste combustion
accounts for about 95% of all the kno~ emissions, with medical and
municipal waste combustion dominating the combustion sources. It
is likely that there are a number of unidentified sources of dioxin in
the U.S. and that we do not have sufficient information about
emissions from known sources to provide precise estimates. It is also
. .
possible that much of the dioxin that contributes to human exposure
results from past dioxin emissions recirculating in the environment
Although there are some natural sources of dioxin, such as forest
fires, it seems clear that dioxins are primarily a' product of modem
industrial society. ··
We believe that the pathway for exposure to humans is
primarily via airborne dioxins that settle on plants, and that are
passed on through the food chain and associated particularly eith
fat. The federal government emphasizes that the benefits· from a
balanced diet far outweigh any theoretical risks from dioxin
exposure.
While the reassessment has been underway, EPA has continued.
to move forward in implementing its dioxin control programs. EPA
has taken action under every one of its major statutes to control the
risks of dioxin, and we believe these activities have made, and will
continue to make, major strides in reducing dioxin emissions. Recent
actions taken by EPA include proposing air emission standards for
municipal waste incinerators, proposing stringent water effluent
standards for pulp and paper mills and waste incinerators. No later
than next February, EPA will propose strict air standards for
reducing dioxin and other emissions from medical waste
incinerators .
While the science of the reassessment is undergoing peer
review, EPA will be examining the reassessment's policy implications
to determine what changes, if any, ·are needed in existing programs.
I want to stress that existing EPA efforts and programs will not be
changed on the basis of this draft reassessment,however, they may
change significantly after the completion of the peer review. EPA is
committed to developing ~ agency-wide strategy· for managing
dioxin risks, concurrent with completion of the dioxin reassessment.
As with the reassessment, we want to provide an opportunity for
early public input into our policy evaluations. This spring, EPA will
hold dioxin policy workshops to explore the policy implications of the
reassessment. The details of these workshops will be announced
later.
This massive scientific effort has made it clear that there are
significant data gaps that are critical to our un9-erstanding and
effective management of dioxin. As a consequence, EPA has begun a
major initiative to expand the understanding of dioxin sources,
environmental pathways and human exposure. Our highest priority
will be to identify additional data to improve the reassessment;
however, the exposure initiative will extend beyond the
reassessment into future years. ,.,
As a part of this effort, today we are calling on all parties to
voluntarily submit any data that can help us better understand dioxin
exposure. The EPA is requesting that industry, public interest .
groups, state and local governments, academia, and hospital
facilities examine their files for existing data. We need information
on dioxin sources, releases and levels in air, water, soil, food, animal
feed, and human tissues. In addition to this voluntary call-in of
existing data, EPA is calling on industries that are potential dioxin
sources to voluntarily work with the Agency to devise and implement
emissions testing programs.
The reassessment represents a major expansion of EP A's
scientific understanding compared to our previous assessments of
dioxin toxicology. Because many of the studies included in the
reassessment have only recently been part of the scientific literature
and our integration of this evidence1s entirely new, it is important
that the reassessment undergo thorough public and scientific peer
review. At the same time, because the general thrust of the
reassessment is consistent with our past scientific basis, we feel
confident in aggressively pursuing our ongoing dioxin control
efforts. This report, once it has completed peer review SOI11etime
next year, ·will give us the best scientific basis possible to guide our
continuing efforts to curb dioxin risks.
\
&EPA
United States ' Environmental Protection
Agency
Dioxin Facts
Communications, Educati0f1.
And Public Affairs
(1700)
New Initiatives .'
September 1 994
In addition to the draft reassessment , EPA has launched two new
initiatives. One will fill major gaps in the understanding of dioxin exposure;
the other will insure a timely policy response to the final reassessment.
Dioxin Data Call-in:
The reassessment reveals significant gaps in the understanding of
dioxin exposure that are critical to effective long-term management of di_oxin
risks. As a consequence, EPA has gone beyond the scope of the reassessment
to begin a major initiative to expand the data and understanding of dioxin
sources, environmental pathways and human exposure. The Agency's
highest priority will be to provide additional data for the completion of the
reassessment; however, the exposure initiative will extend beyond the \
reassessment into future years.
To launch this effort, EPA is calling on all parties to voluntarily submit
any data that can help us better understand dioxin exposure. EPA is
requesting that industry, public interest groups, state and local governments,
academia, and hospital facilities, examine their files for existing data. EPA is
seeking any additional data on dioxin sources, release levels, levels in air,
water and soil, levels in food or animal feed, and levels in human tissues. In
addition to this voluntary call-in of existing data, EPA will be calling on
industries that are potential dioxin sources to voluntarily work with the
Agency to devise and implement emissions testing programs.
Dioxin Policy Workshops
While the science of the reassessment is undergoing peer review, EPA
will be examining the reassessment's policy implications to determine what
changes, if any, are needed in its existing programs. EPA is committed to
developing and completing an Agency-wide strategy for managing dioxin
risks, concurrent with completion of the dioxin reassessment. However,
existing EPA efforts and programs will not be changed on the basis of the draft
reassessment without the completion of the peer review.
As with the reassessment, EPA wants to provide an opportunity for
early public input into its policy evaluations. This spring EPA will hold
dioxin policy workshops to explore the policy implications of the
reassessment. The details of these workshops will be announced later.
&EPA
Un1tec S:a:es
E:iv1ronmen:a: p ,:,teC!1cr
Agency
Dioxin Facts
Comm_wn,cat1or.,s . Ecucat1cr:.
And Pubi,c Att airs (~ :-cc ,
Scientific Highlights from
Draft Reassessment
Scientists from the Environmental Protection Agency, other Federal
agencies and the general scientific community have been involved in a
comprehensive, scientific reassessment of dioxin and related compounds since
1991. External review drafts of the reassessment documents entitled
''Estimating Exposure to Dioxin and related Compounds" and "Health
Assessment -of 2,3,7,8-tetrachloro-p-dibenzodioxin (TCDD) and Related
Compounds" are now being made available by the Agency for public comment
and review by the EPA's Science Advisory Board (SAB).
The exposure document provides the first comprehensive survey of
U.S. sources of dioxin and related compounds. A large variety of sources of
dioxin have been identified and others may exist. The available information
suggests that the presence of dioxin-like compounds in the environment has
occurred primarily as a result of industrial practices and is likely to reflect
changes in release over time. The principal identified sources of
environmental release may be grouped into four major types: Combustion
and Incineration Sources; Chemical Manufacturing/Processing Sources;
Industrial/Municipal Processes; and Reservoir Sources. Because dioxin-like
chemicals are persistent and accumulate in biological tissues, particularly in
animals, the major route of human exposure is ·through ingestion of foods
containing minute quantities of dioxin-like compounds. This results in wide-
spread, low-level exposure of the general population to dioxin-like
compounds. Certain segments of the population may be exposed to additional
increments of exposure by being in proximity to point sources or because of
dietary practices. The levels of dioxin and related compounds in the
environment and in food in the U.S. are based on relatively few samples and
must be conside~e<:f quite uncertain. However, they seem consistent with
levels measured J."h a studies in Western Europe and Canada. The consistency
of these levels across industrialized countries provides reassurance that the
✓ U.S. estimates are reasonable. Collection of additional data to reduce
uncertainty in U.S. estimates of dioxin-like compounds in the environment
and in food is an important need and such data collection is currently
underway in a study being carried out by EPA, FDA and USDA scientists.
The new assessment adopts·the hypothesis that the primary mechanism
by which dioxin-like compounds enter the terrestrial food chain is via
atmospheric deposition. Dioxin and related compounds enter the atmosphere
directly through air emissions or indirectly, for example, through
volatilization from land or water or from re-suspension of p~ticles.
Deposition can occur directly on to soil or on to plant surfaces. At present, it is
· unclear whether atmospheric deposition represents primarily current
contributions of dioxin and related compounds from all media reaching the
. atmosphere or it represents past emissions of dioxin and related compounds
which persist and recycle in the environment. . Understanding the
relationship between these two scenarios will be particularly important in
understanding the relative contributions of individual point sources of these
compounds to the food chain and assessing the effectiveness of control , ..
strategies focussed on either current or past emissions of dioxins in attempting
to reduce dioxin exposures.
Throughout this reassessment, concentrations of dioxin and related
compounds have been presented as 2,3,7,8-tetrachloro-p-dibenz.odioxin
(TCDD) equivalents (TEQs). One compound, 2,3,7,8-TCDD is the best studied
of this class of compounds and is the reference compound with regard to
toxicity equivalence. The strengths and weaknesses as well as the.
uncertainties associated with the TEF /TEQ approach have been discussed in
the report and remain controversial. As noted, the use of the TEQ approach is
fundamental to the evaluation of this group of compounds and as such
represents a key assumption upon which many of the conclusions in this
characterization hinge.. ·
The term ''background" exposure has been used throughout this
reassessment to describe exposure of the general population, which is not
exposed to readily identifiable.point sources of dioxin-like oompounds. Data ·
on human tissue levels suggest that body burden levels among industrialized
nations are reasonably similar. Average background exposure leads to body
burdens in the human population which average 4o-60 pg TEQ/ g lipid (this
equates to 40-60 ppt) when all dioxins, furans and dioxin-like PCBs are
included. High-end estimates of body burden of individuals in the general ..
population (approximately the top 10% of the general population).may be ....
greater than 3 times higher. ·
In addition to general population exposure, some individuals or groups
of individuals ~ also be exposed to dioxin-like compounds from discrete
sources or path~ys locally within their environment Examples of these
"special" exposures include: occupational exposures, direct or indirect
exposure of local populations to discrete sources, exposure of nursing infants
from mother's milk, or exposures of subsistence or recreational fishers.
Although daily exposures to these populations may be significantly higher
than daily exposures to the general population, simply evaluating these
exposures as average daily intakes pro-rated over a lifetime might obscure the
potential significance of elevated exposures for these sub-populations,
particularly if exposures occur for a short period.of time during critical times
during growth and development of children.
-' This reassessment concludes that the scientific community has
identified and described a series of common biological steps that are necessary
for most if not all of the observed effects of dioxin and related compounds in
vertebrates including humans. Binding of dioxin-like compounds to a
cellular protein called the "Ah receptor'' represents the first step in a series of
events attributable to exposure to dioxin-like compounds including
biochemical, cellular and tissue-level changes in normal biological processes.
Binding to the Ah receptor appears to be necessary for all well-studied effects
of dioxin but is not sufficient, in and of itself, to elicit these responses. The
effects elicited by exposure to 2,3,7,8-TCDD are shared by other chemicals
which have a similar structure and Ah receptor binding characteristics.
Consequently, the biological system responds to the cumulative exposure to
other dioxin-like chemicals rather than to the exposure to any single dioxin-
like compound. Based on our understanding of dioxin mechanism(s) to date,
it is accurate to say that interaction with the Ah receptor is .necessary, that at
appropriate doses humans are likely to respond with many of the effects of
dioxin demonstrable in laboratory animals, and that there is likely to be a
variation between and within species and between tissues in individual
species based on differential responses 11down stream" from receptor binding.
The reassessment also finds that there is adequate evidence based on all
available information, including studies in human populations as well as in
laboratory animals and from ancillary experimental data, to support the
inference that humans are likely to respond with a broad spectrum of effects
from exposure to dioxin and related compounds, if exposures are high
enough. The mechanistic relationships of biochemical and cellular changes
seen at very low levels of exposure to production of adverse effects detectible
at higher levels remains uncertain and controversial. These effects will likely
range from adaptive changes at or near background levels of exposure to
adverse effects with increasing severity as exposure increases above
background levels. Enzyme induction, changes in hormone levels and
indicators of altered cellular function represent examples of biomarkers of
exposure of unknown clinical significance which may or may not be early
indicators of toxic response. Induction of activating/metabolizing enzymes at
or near backgro~d levels, for instance, may be adaptive or may be considered
adverse since induction may lead to more rapid metabolism and elimination
of potentially toxic compounds, or may lead to increases in reactive
intermediates and may result in toxic effects. Demonstration of examples of
both of these situations is available in the published literature. Clearly adverse
effects including, perhaps, cancer may not be detectable until exposures exceed
background by one or two orders of magnitude (10 or 100 times).
It is well known that individual species vary in their sensitivity to any
particular dioxin effect. However, the evidence available to date indicates that
humans most likely fall in the middle of the range of sensitivity for
individual effects among animals rather than at either extreme. In other
words, evaluation of the available data suggests that hum~; in general, are
neither extremely sensitive nor insensitive to the individual effects of dioxin-
like compounds. Human data provide direct or indirect support for
evaluation of likely effect levels for several of the endpoints discussed in the
reassessment although the influence of variability among humans remains
difficult to assess. Discussions have highlighted certain prominent,
biologically significant effects of TCDD and related compounds. These
biochemical, cellular, and organ-level endpoints have been shown to be ''
affected by TCDD, but specific data on these endpoints do not generally exist for
other congeners. Despite this lack of congener specific data, there is reason to
infer that these effects may occur for all dioxin-like compounds, based on the
concept of toXIcity equivalence.
Some of the effects of dioxin and related compounds such as enzyme
induction, changes in hormone levels and indicators of altered cellular
function have .been observed in laboratory animals and humans ..at or near
levels to which people in the general population are exposed. Other effects are
detectable only in highly exposed populations, and there may or may not be a
likelihood of response in individuals experiencing lower levels of exposure.
Adverse effects associated with temporary increases in dioxin blood levels
based on short term high level exposures, such as those that might occur in an
industrial accident or in infrequent contact with highly contaminated
environmental media, may be dependent on exposure coinciding with a
window of sensitivity of biological processes.
Subtle changes in biochemistry and physiology such as enzyme
induction, altered levels of circulating reproductive hormones, or reduced
glucose tolerance, have been detected in TCDD-exposed men in a limited
number of available studies. These findings, coupled with knowledge derived
from animal experiments, suggest the potential for adverse impacts on
human metabolism, and developmental and/ or reproductive biology, and,
perhaps, other effects in the range of current human exposures. Given the ·
assumption that TEQ intake values represent a valid comparison with TCDD
exposure, some of these adverse impacts may be occurring at or within one
order of magnitude of average background TEQ intake or body burden levels.
As body burden§increase within and above this range, the probability and
severity as well as the spectrum of human non-cancer effects most likely
increases. It is not currently possible to state exactly how or at what levels
humans in the population will respond but the margin of exposure (M-0-E)
between background levels and levels where effects are detectable in humans
in terms of TEQs is considerably smaller than previously estimated. These
facts and assumptions lead to the inference that some more highly exposed
members of the general population or more highly exposed, special
populations may be at risk for a number of adverse effects including
developmental toxicity based on the inherent sensitivity of the developing
organism to changes in cellular biochemistry and/ or physio~ogy, reduced
reproductive capacity in males based on decreased sperm C9unts, higher
probability of experiencing endometriosis in women, reduced ability to
withstand an immunological challenge and others. This inference that more
highly exposed members of the population may be at risk for various non-
cancer effects is supported by observations in animals, by human information
from highly exposed cohorts for some endpoints and by scientific inference.
The deduction that humans are likely to respond with non-cancer··-·
effects from exposure to dioxin-like compounds is based on the fundamental
level at which these compounds impact cellular regulation and the broad
range of species which have proven to respond with adverse effects. Since, for
example, developmental toxicity following exposure to TCDD-like congeners
occurs in fi$h, birds, and mammals, it is likely to occur at some level in
humans. It is not currently possible to state exactly how or at what levels
people will respond with adverse impacts on development or reproductive
function. Fortunately, there have been few human cohorts identified with
TCDD exposures in the high end of the exposure range, and when these
cohorts have been examined, few clinically significant effects were detected.
The lack of adequate human information and the focus of most currently
available epidemiologic studies on occupationally, TCDD-exposed adult males
makes evaluation of the inference, that non-cancer effects associated with
exposure to dioxin-like compounds may be occurring, difficult. It is important
to note, however, that when exposures to very high levels of dioxin-like
compounds have been studied, such as in the Yusho and Yu-Cheng cohorts, a
spectrum of adverse effects have been detected in men, women and children.
Some have argued that to deduce that a spectrum of non-cancer effects will
occur in humans in the absence of better human data overstates the science;
most scientists involved in the reassessment as authors and reviewers have
indicated that such inference is reasonable given the weight-of-the-evidence
from available data. As presented, this logical conclusion represents a testable
hypothesis which may be evaluated by further data collection.
The likelihood that non-cancer effects may be occurring in the human
population at environmental exposure levels is often evaluated using a
"margin of exposure" (MOE) approach. A MOE is calculated by dividing the
human-equivalefu animal LOAEL or no observed adverse effect level
(NOAEL) with the human exposure level. MOEs in range of 100 -1000 are
generally considered adequate to rule out the likelihood of significant effects
occurring in humans based on sensitive animal responses. The average levels
of intake of dioxin-like compounds in terms of TEQs in humans described
above would be well within a factor of 100 of levels representing lowest
observed adverse effect levels (LOAEI..s) in laboratory animals exposed to
TCDD or TCDD equivalents. For several of the effects noted in animals, a
,, MOE of less than a factor of ten, based on intake levels or body burdens, is
likely to exist.
With regard to carcinogenicity, a weight-of-the-evidence evaluation
suggests that dioxin and related compounds (CDDs, ·coFs, and dioxin-like
PCBs) are likely to present a cancer hazard to humans. While major
uncertainties remain, efforts of this reassessment to bring more data into the
evaluation of cancer potency have resulted in a risk specific dose estimate (1 X
10-6 risk or one additional cancer in one million exposed) of approximately
0.01 pg TEQ/ kg body weight/ day. This risk specific dose estimate represents a
plausible upper bound on risk based on the evaluation of animal and human
data. This value is similar to previous estimates based on less data. "I'rue"
risks are not likely to exceed this value, may be less, and may even be zero for
some members of the population. The epidemiological data alone are not yet
deemed sufficient to characterize the cancer hazard of this class of compounds
as being ''known." However, combining suggestive evidence of recent
epidemiology studies with the unequivocal evidence in animal studies and
inferences drawn from mechanistic data supports the characterization of
dioxin and related compounds as likely cancer hazards, that is, likely to
produce cancer in some humans under some conditions. It is important to
distinguish this statement of cancer hazard from the evaluation of cancer risk.
The extent of cancer risk will depend ori such parameters as route and level of
exposure, overall body burden, dose to target tissues, individual sensitivity
and hormonal status.
The current evidence suggests that both receptor binding and most early
biochemical events such as enzyme induction are likely to demonstrate low-
dose linearity. The mechanistic relationship of these early events to the
complex process of carcinogenesis remains to be established. If these findings
imply low-dose linearity in biologically-based cancer models under
development, then the probability of cancer risk will be linearly related to
exposure to TCDD at low doses. Until the mechanistic relationship between
early cellular responses and the parameters in biologically based cancer models
is better understood, the shape of the dose-response curve for cancer in the
low-dose region can only be inferred with uncertainty. Associations between
exposure to dioxin and certain types of cancer have been noted in occupational
cohorts with average body burdens of TCDD approximately 2 orders ,of
magnitude (100 times) higher than average TCDD body burdens in the general
population. The ~verage body burden in these occupational cohorts level is
within 1-2 orders-of magnitude (10-100 times) of average background body
burdens in the general population in terms of TEQ. Thus, there is no need for
large scale low dose extrapolations. Nonetheless, the relationship of apparent
increases in cancer mortality in these populations to calculations of general
population risk remains uncertain.
TCOD has been clearly shown to increase malignant tumor incidence in
laboratory animals. In addition, a number of studies analyzed in this
reassessment demonstrate other biological effects of dioxin related to the
II
I
process of carcinogenesis. Initial attempts to construct~ biologically-based
model for certain dioxin effects as a part of this reassessment will need to be
continued and expanded to accommodate more of the available biology and to
apply to a broader range of potential health effects associated with exposure to
dioxin-like compounds.
Based on all of the data reviewed in this reassessment and scientific
inference, a pi~e emerges of TCDD and related compounds as potent
toxicants in animals with the potential to produce a spectrum of effects. Some
of these effects may be occurring in humans at very low levels and some may
be resulting in adverse impacts on human health. The potency and
fundamental level at which these compounds act on biological systems
appears to be analogous to several well studied hormones. Dioxin and related
compounds have the ability to alter the pattern of growth and differentiation
of a number of cellular targets by initiating a series of biochemical and
biological events resulting in the potential for a spectrum of responses in
animals and humans. Despite this potential, there is currently no clear
indication of increased disease in the general population attributable to dioxin-
like compounds. The lack of a clear indication of disease in the general
population should not be considered strong evidence for no effect of exposure
to dioxin-like compounds. Rather lack of a clear indication of disease may be a
result of the inability of our current data and scientific tools to directly detect
effects at these levels of human exposure. Several factors suggest a need to
further evaluate the impact of.:these chemicals on humans at or near current _
background levels. These are: the weight of the evidence on exposure and
effects; an apparently low margin-of-exposure for non-cancer effects; and
potential for additivity to background processes related to carcinogenicity.
&EPA
United States
Environmental Protection
· Agency
Dioxin Facts
J
Communications, Education,
And Public Affairs
(1700)
September 1994
EPA'~ ·-On-Going Regulatorr.: Program
Since the 1970's, when dioxin contamination first came to light, EPA has .
established extensive and active control measures for dioxins and furans in each of
its inajor programs.
Oean Air Program v -
On September 1, 1994, Administrator Browner announced proposed air
standards for new and existing municipal waste incinerators, which are estimated to ,
.be the second largest source (behind medical waste incinerators) of the known
annual national air emissions of dioxin. The proposal specifies technology-based
performance standards, which would reduce dioxin and other orgahic chemical
emissions by 95 to 99 percent from 180 existing municipal waste incinerators; dioxin
emissions from new plants would be reduced by more than 99 percent. When the
proposal becomes a final rule in September 1995, existing plants will have one to
three years to comply with the rule, while new plants must comply immediately on
start-up of operations. In the meantime, EPA is working with ~unicipal
.incinerator operators to ensure that they employ good operating procedures to
. -minimize their emissions. ·
. .
EPA will propose similar regulations for medical waste incinerators no later
than February 1, 1995, and issue the final standards by April 15, 1996. There are over
5000 medical waste incinerators in the United States and collectively they are .
estimated to be the largest overall contributor. of known annual national air
-emissions of dioxin; -individually, however, emissions from medical waste
incinerators are thought to be relatively small. Once these regulations are fully
implemented, municipal and medical waste. incinerators will represent only a small .
percentage of ~e currently known annual national air emissions of dioxin._
EPA.is currently also implementing the new.air toxics provisions of the Clean
Air Act Amendments of 1990 that will result in new technology-based air toxics
standards for 170 industrial categories. Where dioxins and furans are significant
. pollutants for those ?tegories, these standards will result in further controls ~n
their emissions.· · · ·
Hazardous Waste Program
The incineration of hazardous wastes may result in dioxin emissions from
burning dioxin-contaminated wastes, or as a result of the incomplete combustion of
other hazardous wastes. EPA regulates the incineration of hazardous wastes,
including any resulting air emissions, under its hazardous waste program.
1
In May 1993, Administrator Browner announced a program to upgrade
emission standards for hazardous waste,combustors, whkh include incinerators,
boilers and industrial furnaces that burn hazardous wastes. The proposed standards
are expected to require stringent, state-of-the-art controls on emissions, which could
· reduce current dioxin emissions from existing hazardous waste combustors by 94 to
97 percent~ EPA plans to propose the new standards in September 1995 and issue the
final standards in December 1996.
_ In the interim, any facility that applies for a new permit or to renew an .
existing permit to burn hazardous wastes will have to conduct a comprehensive risk
assessment to evaluate potential population exposures to hazardous contaminants
. at the facility. EPA will use its existing permitting authority to impose additional
restrictions, including dioxin limits, in such facility permits, if a risk assessment
. shows that additional restrictions are necessary to protect human health and the
environment. • I
The existing regulations require that hazardous waste combustors _ _
. demonstrate that they effectively destroy the wastes being burned and that they _
minimize emissions resulting from the incomplete combustion of h~dous
wastes. Accordingly, hazardous waste combustors must_ conduct a rigorous trial
burn to demonstrate that they can achieve a destruction and removal efficiency of
99.99% for each principal organic hazardous constituent designated in their
operating permits. Hazardous waste combustors that burn dioxin-contaminated
wastes must demonstrate a destruction and removal efficiency of 99.9999% on those
p~incipal organic hazardous constituents that are harder to burn than dioxins and
furans. Hazardous waste c:ombustors must also meet strict limits· on carbon ,
monoxide or hydrocarbon emissions, which· are· signs of poor combus_tion, to
minimize the production of dioxin emissions and other undesirable products of
_incomplete combustion. Finally, hazardous waste combustors must monitor their
-emissio~ frequently to ensure that thef are meeting tneir emission limits .
• • .I -. -.. . . . . . . . . -. -. : . . /_. .·· · .. ' . ,:· .: ·.,
EPA h~_ had ~--active pr~griim to limit dioxin contamination of p'..S. wat~s _ --
-by dev_eloping technology-based effluent limitation guidelines for pulp arid paper_ : ' _ ~::
· ~; which are· incorporated into operating permits for these facilities, developing . -~ __ . '. :
ambient water quality criteria guidance for use by the states in setting water quality · ·-· • ·.
standards for specific water uses, and prohibiting the discharge of dredged material
that is _ contaminated with dioxin in yio~ation of ~tate water quality standards. · . . •-. .·. : . . . . ---.. . . .
On October 3i, 1993, Admhtlstrator Browner prop·osed effluent limitations
guidelines for pulp and paper Iajlls, which create dioxin primarily as a result of the
bleaching of wood pulp used to make paper.: The proposed effluent guidelines.
would require the use of best available technology and would result in major
process changes in the pulping and bleaching technologies used at four categories of
2
·, ... --
'
" ,
/
1 • ' , ...
pulp and paper mills. Process changes in the pulping technology would reduce the
amount of lignin, a precursor to dioxin formation, in pulp prior to bleaching.
Bleaching process changes would substitute chloririe dioxide for elemental chlorine ·
for kraft mills, to reduce dioxin formation, and totally chlorine-free bleaching for
sulfite mills. · ·
In 1984, EPA recommended ambient water quality criteria for 2,3,7,8-TCDD,
the most toxic form of dioxin, to be used by the states in setting enforceable water
quality standards for specific water uses .. The r~mmended ambient water criteria
are based on a cancer risk level of a one in one million (0.013 parts per quadrillion of
dioxin in water). Enforceable water quality standards for dioxin have now ~ ..
either adopted in all 57 sta~s, territories and Indian tribes. that administer the ·water
quality standards program, or imposed by' EPA by regulation. . · .·· .· -· · · . ' . .· .. . ·, .
The Agency is also in the process of establishing water quality criteria for toxic .
pollutants in the Great Lakes. In April 1993, Administrator Brown~ proposed the
Great Lakes Water Quality Guidance; which would establish water ·quality criteria
for 2,3,7 ,8-TCDD to protect both human health and wildlife. The proposed criteria
for dioxin take into consideration the bioaccumulation of dioxin and the risks to
humans and wildlife through the food .chain. 'EPA platlS to issue the final Great
~es Water.Quality Guidance in March 1995. · -· · ·;i· · ·
• • # • .I
. The presence o~ dioxin in river sedm:tents may be-a significant issue _in the .
dredging of harbor entrances. of rivers. EPA and the U.S. Army Corps of Engineers
jointly administer a permit program, ·which regulates the _discharge of dredged and
fill material ~to waters of the United States: including wetlands. If testing of the .. _.,.·.
dredged sediments indicates that dioxin is present, then the sediments must ~eet . . .
the applicable state wa~ ~ty stanclards for dio,cin before they can be. discharged_ ... -
into the waters of the United' States. ·. · -: .· :· ·r •. · · , , •· .. ! .. : . _ . .r .· _ .
' : . . : ~; .•. •; 1:,),
. . . · .' '·: , Safe Drhtl<lng Water Progrant · : ·_ .· ..
. . -. -oil j~y 17, 1~~~-~~ est~blishe~f~~-~a~r s·;~d~ds f~/2,3~1,s-'icoo in · < ... ·. ·
public drinltjng water supplies:. an enforceable maximt#n.-contaminant'level (MCL).' .· .· .·-.1
.;
of 3 x 10~8 nillligr~ per liter. _.This ·1~vel repres~~ 'the lowest' detection level _that"\.: ·. , , · · ·" ·
can be reliably a~~ved within specified limits.of precision and accuracy· during ·_,'~-:_' .:·. : \• _ -·. .
routine laboratory operating conditions ... · Finally, _EPA~identifi¢ granular activated ·.~ . · . : ,,
carbon treatment as the best available techn~logy to be used by publi~ water ·s1;1pply ~ · · ; .. :· · _ .
systems to meet this dioxin level. . ·. · · ,-· _ _· . ,_ .· . · . . -.
.I • • l ' ~ • ·, . '
· -·. ·. .--. · · ·.:_ :::\ ·;_: , Su~erfunci'Program "-._. · .
. . · . . EPA h~ identified dioxin as a key contaminant of ~n~ at approxhnately
two dozen waste disposal sites on the National Priorities List (NPL), which are · ·
scheduled for long-term cleanup under Superfund remedial authority. EPA has
also identified dio~ as an important contaminant in approximately 50 removal
3
actions, which are generally smaller, more immediate cleanups than those involved
at NPL sites.
. . . ~
Actions under Superhmd have included the cleanup of pesticide and Agent
Orange manufacturing plants; industrial facilities that once produced
trichlorophenol; creek sediments and drainage sewers near Love Canal;
contaminated soil from the Tunes Beach sites in Missouri; dioxin wastes improperly
disposed of on farmlan~ in the Midwest;· and dioxin contaminated streets near a
pesticides manufacturing plant. in Newark. ·
. . . . v
Incineration of hazardous substances at Superfund sites, whether of dioxins
_ or other t:hlorinated contaminants, can produce dioxin emissions due to incomplete
combustion. Superfund incineration remedies comply fully "With the existing
r~ations for hazardous waste combustors that ar~ discussed above, including a
rigorous tri;µ burn and frequent monitoring during operation.
' . . . . .
. ' Pesticide and Toxic Chemicals Pr~grani .. ·
. ; ., .
Dioxin first came to -the Federal Government's attention as a contaminant of -
the herbicides 2,4,5-T and S~vex. During the 1;970's and early 1980's these two
herbicides were removed from the market for all uses. ·
Subsequently, EPA began a review of all exi~ting.pesticides· to determine
whether dioxin/furans were created during their manufacturing process_. In 1987,
· EPA initiated two data call-ins that requested specific information regarding the
manufacture of 161 pesticide active ingredients~ . . . _. .
. ,·· .. .---. . . . : .. . . . ;_ . . . . _, .' . . . .
__ · At this time, EPA has ruled out any con~ for 140 .of those_ activ~ pesticide
ingredi~ts because either no dioxin/furan impurities were found _or those active
ingredients are no, longer produced. _ ,-.
-. Of the remaining 21 active pestjcide ingredients, two were found to·have
manufacturing processes which produced detectable_ levels of dioxin/furans, but
_ these levels were_ below the level requiring action. · The manufacturing processes of _·
two other active ingredients are also known·to produce dioxin/furans above.. ·
detectable levels; but their toxicological significance is still un<:fer review. ··EPA is
-.-currently_reviewing the data submitted ~or· the last 17 active ingredients and
_anticipate; ~tit will complete its review by 1996.
0
,·-:.. -•
-·. ·:t-·· .
· -For all new pesticide registrations, ·EPA currenµy evaiuates product ch~try
data to ensure that new active ingredients are screened for dioxin/furan
contamination.
EPA has also been concerned that certain commercial_ chemicalsmight'be
contaminated with dioxins just as certain pesticides have been and has taken actions
to deal with this problem. In 1987, EPA issued the Dioxin/Furan Test Rule pursuant
4
to the Toxic Substances Control Act requiring the submission of data on over sixty
chemicals and chemical precursors already in use that potentially had dioxin
contamination. Of the chemicals tested, four were determined to have dioxin
contamination: chloranil and three brominated flame ret~dants. The
manufacturers and importers of chloranil have agreed to reduce the level of dioxin
in their product and EPA is reviewing the data on the brominated flame retardants
to determine the seriousness of the risk they may pose.
Since 1989, EPA has reviewed new chemical submissions for the potential for
dioxin contamination under its New Chemicals Program. To date, thr~e chemical~
have been tested (none of these have subsequently been commercialized), ten '
. chemicals have been withdrawn (in part because of EP A's requirement for testing)~
. and testing is underway on. s~yeral additional chemicals. · ·
' ..
'· . : .• I ,•• •
·.·.· .....
. • i'.
, '.
.5
' .· .. ,·~ . . -,.,.
United States .
Environmental Protedion
Agency
Communications. education,
And Public Affairs
(1700)
September 1994
,.I ~ &EPA Dioxin Facts , .
.· ..
The .Reassessment Process
. . .
On September 13, 1994, EPA released a "public review draft" of its ·
dioxin reassessment. This release marks a mid-point in EP A's effort to
: reevaluate the sdenfific underst~g of ~o,cin. EPA and outside scientists
have worked for over three years to develop the current draft of the
reassessment. Over the next 120 days EPA~ be taking public commel'lts on -
· the draft document. This public comment period Mil be followed by a . .
formal peer review by ~ A's Science Advisory Board. EPA antidpates ·
. completion and release of the revised final reassessment in the fall of-1995.
In April 1991, EPA announced that it would conduct a sdentific
reassessment of the health risks of~-to dio~ and dioxin'."'like
compqunds. EPA has undertaken this task in light of significant advances in our sden~c: understanding of mechanisms of dioxin toxi~ty, significant ·new
· studies of dio,_an's cardnogenic potential in humans and increased evidence
of :other adverse health effects. 11,e· reassessment is part of the;Agency's goal ·
. to improve its research and science ~ and to incorporate this knowledge :. ·
into EPA decisions. . ·. · . . , . . ,._ •. · · , · . . . -:
. · In 1985 EPA. completed an -~assessment of 2,3,7,8-Tetrachlorodibenzo-p-
dioxin (2,3,7,8-TCDD). In that assessmellt EPA concluded that 2,3,7,8-TCDD is
. a probable human carcinogen. In 1988, the Agency .prepared a draft .· . .
reassessment of the human health. risks from environmental exposures to _
dioxin..· Also, in 1988, ·a draft exposure document ~ prepared ·that presented
procedures for conducting site-specific exposure assessments . for dioxin-like .
compounds. These aSsessments 11Vere re.viewed by the Agency's. Science ·
. Advisory Board (SAB). -In reviewing the draft document the SAB suggested .
. there could be a substantial improvem~t over the then-existing approa~ to
.. analyzing dose respoi:u;e. The Agency was asked to explore the development
.of such.a method.· The current reassessment activities are in response to this · · · : . request · · . . • . •. · · · .. : ·· ·' · · .: · · ,.: : · . · · · · · ·, :. ; ·.·-· ' ~-· .:,,_ : ~ '· · ·_ · · ·: _: • • EPA has ~orked to ~-
7
~ phase. of the 't&xiii· ~m~t _an • •: ·_ -
. open and partidp•tory proces& Th~ _efforts ~ve h:t,cluded _the inv~lvement _ . _
of outside scientists as priridpal authors of sever~ chapters; frequent pupli~. . . . -' · -·
_.· meetings to repo~ progr~s and take.public comment, and publica_tion of early ·
·. drafts for p~blic:.comment and peer review. _Specific activities have included:
. ,• . . -~,· .... -. . . •::. •.-; . •, . ,_. ,· ( . .. -.
. • .On November 15~ 1991; and April 28, 1992, public.meetings were held .. ·
· to inform the public of the Agency's plans arid activities for ·the · -
. reassessment, to hear m;td receive public comments and reviews of the .
·proposed plans, and to receive any current, scientifically relevant .
-information. ·
• In the fall of 1992, the Agency convened two peer-review workshops to
review early drafts of our work. The first peer-review was held
September 10 and 11, 1992, and reviewed a draft of the exposure
assessment. The second peer.;.review was held September 22-23, 1992,
_ and reviewed eight chapters of the Health Assessment Document . On
September 24-25, at a special workshop involving participants for the
-two previous peer-reviews, those scientists were asked to identify
issues and offer guidance for drafting the risk characterization.
• On September 7 and 8, 1993, a third peer-review workshop was held to ·
· review a draft of a revised and expanded Epidemiology and Human
-Data Chapter. , · · · : . . . _
• . During the spring and summer of 1994, EPA circulated revised drafts 9f
all chapters of the reassessment _for review by scientists in other Federal
'agencies and a special panel of scientists from EPA, USDA, and m-IS .
was convened to carefully review the risk_characterization chapter.
. . .
Ori September 13, 1994, the EPA released the public review draft of the
full reassessment. The reassessment consists of two documents, each about a
. thousand pages long, and each published in several volumes. . One of these
documents addresses-the human health effects of dioxin; the second focuses
on· sources and levels of exposure. The reassessment is a scientific document
. and does not address policy or regulatory issues. Volume three of the health
effects document is the Risk Characterization chapter • This c:1'.tapter
. integrates the findings of both the effects and exposure documents, and
describe the potential risks posed by. dioxin. _
Starting on September 13 and for the following 120 days the EPA will be
taking public comments on the draft document.·_ . During the public comment
period, public meetings will be· convened to take formal comments on the
· draft documents. These hearings are being planned -for the firit two weeks of ·
December in five areas: Washington, DC; Chicago, n.; Dall~, TX; San -·
.Francisco, CA and New York/New Jersey Detailed information will be •
provided in a future Fecieral Register notice. . -· . · · · · --·_. _ · ·,
The draft cloaiments also wiQ. receive ~entific peer review by EP A's
Science Advisory ~ard. · This meeting will be held after the public comment
_ . period has ended, early next yeaf. Info~ation about this meeting will be .
published in a future Federal Register notice. -.
Following SAB revjew,·comments and revisions· will be incorporated
• · and final documents will be issued. We anticipate completion and release of
the final reassessment about' one year from now in the fall of 1995. ' .
..
Reassessment or Dioxin -External Review Drafts • Contents
The following information is provided to assist you in locating information contained in the two
external review drafts for dioxin. ·
Health Assessment Document ror
2~,7,8-Tetrachlorodibemo-p-dloxin (TCDD)
and Related Compounds
(EPA/600/BP-92/00la, 001b, 001c)
Volume I of ill (EPA/600/BP-92/00la):
Chapter 1.
Chapter 2.
Chapter 3.
Chapter 4.
Chapter 5.
Chapter 6.
Disposition and Pharmacokinetics
Mechanisms of Toxic Actions
Acute, Subchronic, and Chronic Toxicity
Immunotoxic Effects
Reproductive and Developmental Toxicity
Carcinogenicity of TCDD in Animals
Volume II of ill (EPA/600/BP-92/00lb):
Chapter 7.
Chapter 8.
Epidemiology /Human Data
Dose-Response Relationships
Volume ID of m (EPA/600/BP-92/00lc):
Chapter 9. Risk Characterization (Note: This third volume of the 3-volume set
integrates health and exposure information on dioxin and related
compounds; approx. 100 pages.)
Estimating Exposure to Dioxin-Uke Compounds
(EPA/600/6-88/00SCa, OOSCb, OOSCc)
Vc;,lume I of III (EPA/600/6-88/00SCa): Executive Summary (Note: This first volume of the
3-volume set summarizes the exposure information on
dioxin and related compounds; approx. 100 pages.)
Volume II of III (EPA/600/6-88/00SCb):
Volume III of III (EPA/600/6-88/00SCc):
Properties, Sources, Occurrence, and Background
Exposure
Site-Specific Assessment Procedures
Reassessment or Dioxin -External Review Drafts -How to Order
If you wish to receive copies of any of the volumes of the draft dioxin reassessment, please complete
the bottom of this page and mail, fax, or phone the Center for Environmental Research Information (CERI)
(see address and phone numbers below). Due to the large size of the reassessment (over 2,000 pages in
length) and the expense of printing and mailing, please check only the document that you actually need from
the following list.
•
•
Risk Characterization Chapter, EPA/600/BP-92/00lc (paper)
Risk Characterization Chapter, EPA/600/BP-92/00lca (disk)
(Note: This is Volume III of the 3-volume set; it integrates health and exposure information on dioxin
and related compounds; approximately 100 pages.)
OR
Health Assessment Document for 2;3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) and Related
Compounds, Volumes I, II, and Ill, EPA/600/BP-92/00la, 001b, 001c.
(Note: The full document is 3 volumes and approximately 1,100 pages.)
AND/OR
Executive Summary of the Exposure Document, EPA/600/6-88/005Ca. (paper)
Executive Summary of the Exposure Document, EPA/600/6-88/005Caa (disk)
(Note: This is Volume I of the 3-volume set; it summarizes the exposure information on dioxin and
related compounds; approximately 100 pages.)
OR
Estimating Exposure to Dioxin-Like Compounds, Volumes I, 11, and III,
EPA/«xJ/6-88/005Ca, Cb, Cc.
(Note: The full document is 3 volumes and approximately 1,300 pages.)
• Both summary volumes will be available as a WordPerfect 5.1 file on a 31n• PC-DOS formatted disk.
Please check paper or disk, not both.
Please print your name and complete mailing address:
Name:
Address:
City, State:
Mail to: CERI/ORD Publications Center
U.S. Environmental Protection Agency
26 W. Martin Luther King Drive
Cincinnati, OH 45268
telephone [phone]; fax [phone]
Zip: -----------
If you have already contacted CERI or responded to the postcard, you need not send this form.
..
EPA AND INTERNATIONAL TEFs
FOR DIOXINS & FURANS
TEF = TOXIC EQUIVALENCY FACTOR
DIOXINS
1.000 X CONC 2,3, 7 ,8-TCDD
0.500 X CONC 1,2,3, 7 ,8-PeCDD
0.100 X CONC 1,2,3,6, 7 ,8-HxCDD
0.100 X CONC 1,2,3, 7 ,8,9-HxCDD
0.100 X CONC 1,2,3,4, 7 ,8-HxCDD
0.010 X CONC 1,2,3,4,6, 7 ,8-HpCDD
0.001 X CONC OCDD
FURANS
0.100 X CONC 2,3,7,8-TCDF
0.050 X CONC 1,2,3, 7 ,8-PeCDF
0.500 X CONC 2,3,4, 7 ,8-PeCDF
0.100 X CONC 1,2,3,6, 7 ,8-HxCDF
0.100 X CONC 1,2,3, 7 ,8,9-HxCDF
0.100 X CONC 1,2,3,4, 7 ,8-HxCDF
0.100 X CONC 2,3,4,6, 7 ,8-HxCDF
0.010 X CONC 1,2,3,4,6, 7,8-HpCDF
0.010 X CONC 1,2,3,4, 7 ,8,9-HpCDF
0.001 X CONC OCDF
21 July 1994 To: Bill Meyer From: Grover Nicholson Subject: Revised Warren County PCB Landfill sampling plan O_aY..J_; s_amn,le_Location Landfill air vent 1) . Sample Number Sample Type Analyses containers~&~Number SPLrr Surface soil near air vent Duplicate of one of above samples Surface soil near pump house Duplicate of one of above samples "5PllT Seep on slope WL-001-AR WL-006-SS to WL-015-SS WL-026-SS WL-016-SS to WL-025-SS WL-027-SS WL-005-SS Air Surface soil Surface soil Surface soil Surface soil Surface soil PCB PCB PCB PCB PCB PCB Charcoal filter 125-ml solid cap 125-ml solid cap 125-ml solid cap 125-ml solid cap 125-ml solid cap 01 10 01 10 01 01 .... ..
Da.Y....£.i. Team_l Sample Location Sample Number Sample Type Analyses Containers& Number Well #1 WL-001-GW Ground water voe 40-ml septum cap 02 svoc 2-liter amber 01 PEST/HERB 2-liter amber 01 PCB with above !NORG 1-liter plastic 01 DIOXIN Triangle Lab :5PLI t Well #2 WL-002-GW Ground water voe 40-ml septum cap 02 svoc 2-liter amber 01 PEST/HERB 2-liter amber 01 PCB with above !NORG 1-liter plastic 01 DIOXIN Triangle Lab Well #3 WL-003-GW Ground water voe 40-ml septum cap 02 svoc 2-liter amber 01 PEST/HERB 2-liter amber 01 PCB with above !NORG 1-liter plastic 01 DIOXIN Triangle Lab S?t.lT Well #4 WL-004-GW Ground water voe 40-ml septum cap 02 svoc 2-liter amber 01 PEST/HERB 2-liter amber 01 PCB with above !NORG 1-liter plastic 01 DIOXIN Triangle Lab Duplicate of WL-005-GW Ground water voe 40-ml septum cap 02 sample WL-004-GW svoc 2-liter amber 01 PEST/HERB 2-liter amber 01 PCB with above !NORG 1-liter plastic 01 .,. ..,
'l.. Da~_; Team 2 Sample Location Sample Number Sample Type Analyses Containers & Number SPLIT Landfill air vent WL-001-LC Landfill contents, voe 125-ml septum cap 01 e dry svoc 125-ml solid cap Ol • l)c.,Pt-l(jlt-TE" PEST/HERB 125-ml solid cap 01 PCB 125-ml solid cap 04 !NORG 125-ml solid cap 01 DIOXIN Triangle Lab $PL-IT Landfill air vent WL-002-LC Landfill contents, voe 125-ml septum cap 01 wet svoc 125-ml solid cap 01 PEST/HERB 125-ml solid cap 01 PCB 125-ml solid cap 04 !NORG 125-ml solid cap 01 DIOXIN Triangle Lab Physical Zip lock bag 01 Nutrient Zip lock bag 01 Richneck Creek, WL-001-SW Surface water PCB 2-liter amber 01 upstream WL-001-SD Sediment PCB 125-ml solid cap 01 $ Richneck Creek, WL-002-SW Surface water PCB 2-liter amber 01 Pu T -downstream WL-002-SD Sediment PCB 125-ml solid cap 01 (*'t>) Unnamed Tributary, 2-liter amber WL-003-SW surface water PCB 01 upstream WL-003-SD Sediment PCB 125-ml solid cap 01 Unnamed Tributary, WL-004-SW Surface water PCB 2-liter amber 01 downstream WL-004-SD Sediment PCB 125-ml solid cap 01 Duplicate of WL-005-SW Surface water PCB 2-liter amber 01 WL-004-SW Duplicate of WL-005-SD Sediment PCB 125-ml solid cap 01 WL-004-SD
Day_2_; Team_3 Sample Location Sample Number Sample Type Analyses Containers & Number !>PLIT Leachate pond WL-001-SS Surface soil PCB 125-ml solid cap 01 outlet ravine Leachate pond WL-002-SS Surface soil PCB 125-ml solid cap 01 near outfall Leachate pond WL-003-SS Surface soil PCB 125-ml solid cap 01 middle Leachate pond WL-004-SS Surface soil PCB 125-ml solid cap 01 at filter outfall Duplicate of WL-028-SS Surface soil PCB 125-ml solid cap 01 WL-004-SS Sand filter WL-001-FL Filter medium PCB 125-ml solid cap 01 Charcoal filter WL-002-FL Filter medium PCB 125-ml solid cap 01 r
I' Da~ Team 3 (continued) Sample Location Sample Number Sample Type Analyses Containers & Number SPLIT Filter system WL-001-LE Leachate voe 40-ml septum cap 02 inlet svoc 2-liter amber 01 PEST/HERB 2-liter amber 01 PCB with above INORG 1-liter plastic 01 DIOXIN Triangle Lab Filter system WL-002-LE Leachate voe 40-ml septum cap 02 outlet svoc 2-liter amber 01 PEST/HERB 2-liter amber 01 PCB with above !NORG 1-liter plastic 01 DIOXIN Triangle Lab Air vent WL-003-LE Leachate voe 40-ml septum cap 02 (if possible) svoc 2-liter amber 01 PEST/HERB 2-liter amber 01 PCB with above !NORG 1-liter plastic 01 DIOXIN Triangle Lab Trip Blank WL-001-BL Water VOA 40-ml septum cap 02 Rinseate Blank WL-002-BL Water VOA 40-ml septum cap 02 svoc 2-liter amber 01 !NORG 1-liter plastic 01 Post-Preservative WL-003-BL Water VOA 40-ml septum cap 02 Blank !NORG 1-liter plastic 01
SOURCES WITH TRACE QUANTITIES
OF DIOXINS AND FURANS
FOREST FIRE SMOKE
EXHAUST FROM DIESEL TRUCKS & CARS
SCRAP METAL PROCESSING
CIGARETTE SMOKE
COFFEE FILTERS
PAPER MILK CARTONS
DISPOSABLE DIAPERS
FACIAL TISSUES
WASTE OIL
SEW AGE SLUDGE
07 . 29 . SL3 0 2 : 1 0 PM
Method Name:
Analyte List:
Application:
Methodology:
Calibration Range:
Detection Limits:
(TCDD/fCDF)
Matrices:
Holding Times:
Sample Required:
Lab Blank:
*TRIANGLE LABS P[l2
Product Sheet
Determination of seventeen 2378 substituted
PCDD/PCDFs, plus total Tetra through Octa Homolog
groups in environmental matrices. Regulations include
RCRA, CERCLA and state authorities.
High resolution gaschromatography/high reso1ution mass
spectrometry on purified extracts. Isotope dilution
quantitation. Optional method for toxicity equivalency
factors (TEF).
10-2000 ppq for water (I L) for TCDD/TCDF
1.0--200 ppt for solids (IO g) for TCDD/rCDF
10 ppt water
1.0 ppt soil/sedimenUtissue
20pgPUF
10-500 ppt chemical (contact Client Services)
penta, hexa and hepta congeners multiply by 5, octa
multiply by ten (10).
Water, soil, sediment, oil, tissue, adipose, chemical, ambient
air, (PUF), sludge and others.
30 days for extraction; Analysis within 45 days ofcolJection.
20 grams soil/sediment; 30 grams tissue; 1-Jiter water;
separate duplicate samples shou1d be sent in case of
breakage or reextraction.
One per 20 samples; blank must be analyzed after every
CONCAL that sample batch is run.
Proprietary Information
Ll ,...,1·· • ') 9 q ,, '-. '-' -.) 02 : 1 0 PM
calibration QC:
Mass Calibration:
GC Column Performance:
Initial Calibration:
Continuing Calibration;
Internal Standard
Recoveries:
QC Samples:
Deliverables:
Interfe'rences:
*TRIANGLE LABS
Document instrument resolving power of 10,000.
This solution must.be run at the beginning of the 12 hour
sequence. It documents column resolution of close eluting
TCDDtrCDF isomers, sets retention time windows and
monitors adequate sensitivity. This may be combined with
the continuing calibration.
Twenty (20%) percent RSD for seventeen analytes and
thirty (30%) percent for labeled standards. Signal to noise
for all compound~ must meet 10: 1. 1$otopic ratios must be
within ±15% of theoretical.
Twenty (20%) percent for seventeen anaiytes and 30% for
labeled standard~. Signal to noise for all compounds must
meet 10: 1. Isotopic ratios must be within + 15% of
theoretical.
Twenty five (25%) percent RSD for seventeen analytes and
thirty five (35%) for labeled standards. Signal to noise for
all compounds must meet 10: 1. Isotopic ratios must be
within ±15% of theoretical.
Should be between 40--135%recovery. The signal to noise
must meet 10:1. otherwise the quantitation is invalid.
Surrogates and alternate standards should meet the same
criteria.
Matrix Spike (MS), Matrix Spike Duplicate (MDS) and
duplicates can be done at the option of the client. Percent
recoveries should be between 75-125%. The relative
difference of duplicates should be within 25%.
Reporting levels I, II and III.
Polychlorinated diphenyether channels are monitored, if
Propni:tary information
0 2 : 1 0 PM *TRIANGLE LABS P04
value is reported as an EMPC (estimated maximum possible
concentration). If an analyte fails to meet the
identification criteria of isotope ratio, the value is
also reported as EMPC.
Confirmation: Confirmation of2,3, 7,8-TCDF is required on the DB~225
GC column if detected on the DB-5 column above the
target detection limit.
TLI METHOD MODIFICATIONS:
1. 2,3,7,8-TCDF is confirmed if above the detection limit on primary (DB-5) column
(method specifies if greater than 2.5 to 1 SIN).
2. Polychlorinated Diphenylether interferences quantitated asEMPCifgreaterthan 10%
of peak height of analyte (method specifies if signal ofDPE greater than 2.5 to 1 SIN).
3. If the ending CONCAL is between 20-25% D for analytes and 30-35% for labeled
standards the ICAL RFs is m~ed (method specifies use average of two CONCALs).
4.
5.
6.
Tissue: 20% of extract used for percent LIPID (method specifies 50%).
CON CAL use labeled standards to monitor carry-over, therefore1 method blank does
not need to be rerun on every 12 hour clock.
Dilutions are only run if analytes are saturated.
Proprietary Information
07. 29. 93
........ ,i
02 : 1 0 PM
Dioxin
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6, 7,8-HxCDD
1,2,3, 7,8,9-HxCDD
1,2,3,4,6, 7,8 .. HpCDD
OCDD
*TRIANGLE LABS
Table I
Medthod 8290
Analytes
Analytcs
Furan
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4, 7,8-PeCDF
1,2,3,4, 7,8-HxCDF
1,2,3,6,7,8-HxCDF
I,2,3,7,8,9•HxCDF
2,3,4,6, 7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4, 7,8,9-HpCDF
OCDF
P 05